JP6328791B2 - Organic semiconductor device and compound - Google Patents
Organic semiconductor device and compound Download PDFInfo
- Publication number
- JP6328791B2 JP6328791B2 JP2016559005A JP2016559005A JP6328791B2 JP 6328791 B2 JP6328791 B2 JP 6328791B2 JP 2016559005 A JP2016559005 A JP 2016559005A JP 2016559005 A JP2016559005 A JP 2016559005A JP 6328791 B2 JP6328791 B2 JP 6328791B2
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- organic semiconductor
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- monovalent organic
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- 239000004065 semiconductor Substances 0.000 title claims description 214
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- 125000000962 organic group Chemical group 0.000 claims description 66
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- 229910052760 oxygen Inorganic materials 0.000 claims description 51
- 229910052717 sulfur Inorganic materials 0.000 claims description 51
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 49
- 239000011230 binding agent Substances 0.000 claims description 44
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- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 28
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- 125000000623 heterocyclic group Chemical group 0.000 claims 4
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920012287 polyphenylene sulfone Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- 238000007650 screen-printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XQTUSPVIMZCNPC-UHFFFAOYSA-N thieno[3,4-c]furan-1,3-dione Chemical compound S1C=C2C(=O)OC(=O)C2=C1 XQTUSPVIMZCNPC-UHFFFAOYSA-N 0.000 description 1
- 125000005556 thienylene group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- ZGWZWRHJHVTXEL-UHFFFAOYSA-N trimethyl(thiophen-2-yl)stannane Chemical compound C[Sn](C)(C)C1=CC=CS1 ZGWZWRHJHVTXEL-UHFFFAOYSA-N 0.000 description 1
- HDZULVYGCRXVNQ-UHFFFAOYSA-N trimethyl-(5-trimethylstannylthieno[3,2-b]thiophen-2-yl)stannane Chemical compound S1C([Sn](C)(C)C)=CC2=C1C=C([Sn](C)(C)C)S2 HDZULVYGCRXVNQ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K10/40—Organic transistors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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Description
本発明は、有機半導体素子及びその製造方法、化合物、有機半導体膜形成用組成物、並びに、有機半導体膜に関する。 The present invention relates to an organic semiconductor element and a method for producing the same, a compound, a composition for forming an organic semiconductor film, and an organic semiconductor film.
軽量化、低コスト化、柔軟化が可能であることから、液晶ディスプレイや有機ELディスプレイに用いられるFET(電界効果トランジスタ)、RFID(RFタグ)等に、有機半導体膜(有機半導体層)を有する有機トランジスタが利用されている。
従来の有機半導体としては、特許文献1に記載されたものが知られている。Since it can be reduced in weight, cost, and flexibility, it has an organic semiconductor film (organic semiconductor layer) on FETs (field effect transistors), RFIDs (RF tags), etc. used in liquid crystal displays and organic EL displays. Organic transistors are used.
As a conventional organic semiconductor, the one described in Patent Document 1 is known.
本発明が解決しようとする課題は、移動度のバラツキが少なく、高温によるアニール処理を行わなくても高移動度である有機半導体素子及びその製造方法を提供することである。
また、本発明が解決しようとする他の課題は、有機半導体として好適な新規な化合物を提供することである。
更に、本発明が解決しようとする他の課題は、移動度のバラツキが少なく、高温によるアニール処理を行わなくても高移動度である有機半導体膜、及び、上記有機半導体膜を好適に形成することができる有機半導体膜形成用組成物を提供することである。The problem to be solved by the present invention is to provide an organic semiconductor element having a low mobility variation and a high mobility without performing an annealing process at a high temperature, and a method for manufacturing the same.
Another problem to be solved by the present invention is to provide a novel compound suitable as an organic semiconductor.
Furthermore, another problem to be solved by the present invention is to suitably form an organic semiconductor film having a small mobility variation and a high mobility without performing an annealing process at a high temperature, and the organic semiconductor film. It is to provide a composition for forming an organic semiconductor film.
本発明の上記課題は、以下の<1>、<5>、<10>、<15>、又は、<16>に記載の手段により解決された。好ましい実施態様である<2>〜<4>、<6>〜<9>、<11>〜<14>、及び、<17>〜<20>とともに以下に記載する。
<1> 式1で表される繰り返し単位を有する有機半導体を含有する有機半導体層を有することを特徴とする、有機半導体素子、The above-described problems of the present invention have been solved by means described in the following <1>, <5>, <10>, <15>, or <16>. It is described below together with <2> to <4>, <6> to <9>, <11> to <14>, and <17> to <20>, which are preferred embodiments.
<1> An organic semiconductor element comprising an organic semiconductor layer containing an organic semiconductor having a repeating unit represented by Formula 1,
式1中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、O、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、Y11及びY12が同時にOとなることはなく、R11は一価の有機基を表し、Ar11、Ar12、Ar13はそれぞれ独立に、芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m11は0〜2の整数を表し、m12は0〜4の整数を表し、m13は0〜2の整数を表す、
<2> XがO、S、NR12のいずれかである、<1>に記載の有機半導体素子、
<3> Y11及びY12がいずれもSであるか、いずれもC(CN)2である、<1>又は<2>に記載の有機半導体素子、
<4> 式1で表される繰り返し単位が、式2で表される繰り返し単位である、<1>〜<3>のいずれか1つに記載の有機半導体素子、In Formula 1, X represents any of CR 12 2 , O, S, Se, NR 12 , SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents O, S, N-CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13. R 13 represents a monovalent organic group, a plurality of R 13 may be bonded to each other to form a ring, and Y 11 and Y 12 do not simultaneously become O, and R 11 is a monovalent group. Ar 11 , Ar 12 and Ar 13 each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, and m11 represents an integer of 0 to 2. , M12 represents an integer of 0-4, m13 represents an integer of 0-2,
<2> The organic semiconductor element according to <1>, wherein X is any one of O, S, and NR 12 .
<3> The organic semiconductor element according to <1> or <2>, wherein Y 11 and Y 12 are both S, or both are C (CN) 2 .
<4> The organic semiconductor element according to any one of <1> to <3>, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.
式2中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、O、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、Y11及びY12が同時にOとなることはなく、R11は一価の有機基を表し、Ar12は芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m12は0〜4の整数を表し、X21及びX22はそれぞれ独立に、O、S、Se、NR12’、SiR12’ 2のいずれかを表し、R12’はそれぞれ独立に、水素原子又は一価の有機基を表し、R21〜R24はそれぞれ独立に、水素原子又は一価の有機基を表し、m11’は0〜2の整数を表し、m13’は0〜2の整数を表す、
<5> 式1で表される繰り返し単位を有する化合物、In Formula 2, X represents any of CR 12 2 , O, S, Se, NR 12 , and SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents O, S, N-CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13. R 13 represents a monovalent organic group, a plurality of R 13 may be bonded to each other to form a ring, and Y 11 and Y 12 do not simultaneously become O, and R 11 is a monovalent group. Ar 12 represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m12 represents an integer of 0 to 4, and X 21 and X 22 each independently , O, S, Se, NR 12 ', SiR 12' represents one of the 2, R 12 'each independently represent a hydrogen atom or a monovalent organic group, R 21 to R 24 is To respectively independently represent a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0 to 2, m13' is an integer of 0 to 2,
<5> a compound having a repeating unit represented by formula 1,
式1中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、O、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、Y11及びY12が同時にOとなることはなく、R11は一価の有機基を表し、Ar11、Ar12、Ar13はそれぞれ独立に、芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m11は0〜2の整数を表し、m12は0〜4の整数を表し、m13は0〜2の整数を表す、
<6> XがO、S、NR12のいずれかである、<5>に記載の化合物、
<7> Y11及びY12がいずれもSであるか、いずれもC(CN)2である、<5>又は<6>に記載の化合物、
<8> 式1で表される繰り返し単位が、式2で表される繰り返し単位である、<5>〜<7>のいずれか1つに記載の化合物、In Formula 1, X represents any of CR 12 2 , O, S, Se, NR 12 , SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents O, S, N-CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13. R 13 represents a monovalent organic group, a plurality of R 13 may be bonded to each other to form a ring, and Y 11 and Y 12 do not simultaneously become O, and R 11 is a monovalent group. Ar 11 , Ar 12 and Ar 13 each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, and m11 represents an integer of 0 to 2. , M12 represents an integer of 0-4, m13 represents an integer of 0-2,
<6> The compound according to <5>, wherein X is any one of O, S and NR 12
<7> The compound according to <5> or <6>, wherein Y 11 and Y 12 are both S, or both are C (CN) 2 .
<8> The compound according to any one of <5> to <7>, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.
式2中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、O、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、Y11及びY12が同時にOとなることはなく、R11は一価の有機基を表し、Ar12は芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m12は0〜4の整数を表し、X21及びX22はそれぞれ独立に、O、S、Se、NR12’、SiR12’ 2のいずれかを表し、R12’はそれぞれ独立に、水素原子又は一価の有機基を表し、R21〜R24はそれぞれ独立に、水素原子又は一価の有機基を表し、m11’は0〜2の整数を表し、m13’は0〜2の整数を表す、
<9> 有機半導体である、<5>〜<8>のいずれか1つに記載の化合物、
<10> 式1で表される繰り返し単位を有する化合物と、溶媒とを含む、有機半導体膜形成用組成物、In Formula 2, X represents any of CR 12 2 , O, S, Se, NR 12 , and SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents O, S, N-CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13. R 13 represents a monovalent organic group, a plurality of R 13 may be bonded to each other to form a ring, and Y 11 and Y 12 do not simultaneously become O, and R 11 is a monovalent group. Ar 12 represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m12 represents an integer of 0 to 4, and X 21 and X 22 each independently , O, S, Se, NR 12 ', SiR 12' represents one of the 2, R 12 'each independently represent a hydrogen atom or a monovalent organic group, R 21 to R 24 is To respectively independently represent a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0 to 2, m13' is an integer of 0 to 2,
<9> The compound according to any one of <5> to <8>, which is an organic semiconductor,
<10> A composition for forming an organic semiconductor film, comprising a compound having a repeating unit represented by Formula 1 and a solvent,
式1中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、O、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、Y11及びY12が同時にOとなることはなく、R11は一価の有機基を表し、Ar11、Ar12、Ar13はそれぞれ独立に、芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m11は0〜2の整数を表し、m12は0〜4の整数を表し、m13は0〜2の整数を表す、
<11> XがO、S、NR12のいずれかである、<10>に記載の有機半導体膜形成用組成物、
<12> Y11及びY12がいずれもSであるか、いずれもC(CN)2である、<10>又は<11>に記載の有機半導体膜形成用組成物、
<13> 式1で表される繰り返し単位が、式2で表される繰り返し単位である、<10>〜<12>のいずれか1つに記載の有機半導体膜形成用組成物、In Formula 1, X represents any of CR 12 2 , O, S, Se, NR 12 , SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents O, S, N-CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13. R 13 represents a monovalent organic group, a plurality of R 13 may be bonded to each other to form a ring, and Y 11 and Y 12 do not simultaneously become O, and R 11 is a monovalent group. Ar 11 , Ar 12 and Ar 13 each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, and m11 represents an integer of 0 to 2. , M12 represents an integer of 0-4, m13 represents an integer of 0-2,
<11> X is is O, S, one of NR 12, the organic semiconductor film forming composition as described in <10>,
<12> The composition for forming an organic semiconductor film according to <10> or <11>, wherein Y 11 and Y 12 are both S, or both are C (CN) 2 .
<13> The composition for forming an organic semiconductor film according to any one of <10> to <12>, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.
式2中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、O、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、Y11及びY12が同時にOとなることはなく、R11は一価の有機基を表し、Ar12は芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m12は0〜4の整数を表し、X21及びX22はそれぞれ独立に、O、S、Se、NR12’、SiR12’ 2のいずれかを表し、R12’はそれぞれ独立に、水素原子又は一価の有機基を表し、R21〜R24はそれぞれ独立に、水素原子又は一価の有機基を表し、m11’は0〜2の整数を表し、m13’は0〜2の整数を表す、
<14> バインダーポリマーを更に含有する、<10>〜<13>のいずれか1つに記載の有機半導体膜形成用組成物、
<15> <10>〜<14>のいずれか1つに記載の有機半導体膜形成用組成物を基板上に塗布する塗布工程を含む、有機半導体素子の製造方法、
<16> 式1で表される繰り返し単位を有する化合物を含む有機半導体膜、In Formula 2, X represents any of CR 12 2 , O, S, Se, NR 12 , and SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents O, S, N-CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13. R 13 represents a monovalent organic group, a plurality of R 13 may be bonded to each other to form a ring, and Y 11 and Y 12 do not simultaneously become O, and R 11 is a monovalent group. Ar 12 represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m12 represents an integer of 0 to 4, and X 21 and X 22 each independently , O, S, Se, NR 12 ', SiR 12' represents one of the 2, R 12 'each independently represent a hydrogen atom or a monovalent organic group, R 21 to R 24 is To respectively independently represent a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0 to 2, m13' is an integer of 0 to 2,
<14> The composition for forming an organic semiconductor film according to any one of <10> to <13>, further containing a binder polymer,
<15> The manufacturing method of an organic semiconductor element including the application | coating process which apply | coats the composition for organic-semiconductor film formation as described in any one of <10>-<14> on a board | substrate,
<16> an organic semiconductor film containing a compound having a repeating unit represented by formula 1,
式1中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、O、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、Y11及びY12が同時にOとなることはなく、R11は一価の有機基を表し、Ar11、Ar12、Ar13はそれぞれ独立に、芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m11は0〜2の整数を表し、m12は0〜4の整数を表し、m13は0〜2の整数を表す、
<17> XがO、S、NR12のいずれかである、<16>に記載の有機半導体膜、
<18> Y11及びY12がいずれもSであるか、いずれもC(CN)2である、<16>又は<17>に記載の有機半導体膜、
<19> 式1で表される繰り返し単位が、式2で表される繰り返し単位である、<16>〜<18>のいずれか1つに記載の有機半導体膜、In Formula 1, X represents any of CR 12 2 , O, S, Se, NR 12 , SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents O, S, N-CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13. R 13 represents a monovalent organic group, a plurality of R 13 may be bonded to each other to form a ring, and Y 11 and Y 12 do not simultaneously become O, and R 11 is a monovalent group. Ar 11 , Ar 12 and Ar 13 each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, and m11 represents an integer of 0 to 2. , M12 represents an integer of 0-4, m13 represents an integer of 0-2,
<17> X is O, S, is either NR 12, the organic semiconductor film according to <16>,
<18> The organic semiconductor film according to <16> or <17>, wherein Y 11 and Y 12 are both S, or both are C (CN) 2 .
<19> The organic semiconductor film according to any one of <16> to <18>, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.
式2中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、O、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、Y11及びY12が同時にOとなることはなく、R11は一価の有機基を表し、Ar12は芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m12は0〜4の整数を表し、X21及びX22はそれぞれ独立に、O、S、Se、NR12’、SiR12’ 2のいずれかを表し、R12’はそれぞれ独立に、水素原子又は一価の有機基を表し、R21〜R24はそれぞれ独立に、水素原子又は一価の有機基を表し、m11’は0〜2の整数を表し、m13’は0〜2の整数を表す、
<20> 溶液塗布法により製膜された、<16>〜<19>のいずれか1つに記載の有機半導体膜。In Formula 2, X represents any of CR 12 2 , O, S, Se, NR 12 , and SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents O, S, N-CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13. R 13 represents a monovalent organic group, a plurality of R 13 may be bonded to each other to form a ring, and Y 11 and Y 12 do not simultaneously become O, and R 11 is a monovalent group. Ar 12 represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m12 represents an integer of 0 to 4, and X 21 and X 22 each independently , O, S, Se, NR 12 ', SiR 12' represents one of the 2, R 12 'each independently represent a hydrogen atom or a monovalent organic group, R 21 to R 24 is To respectively independently represent a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0 to 2, m13' is an integer of 0 to 2,
<20> The organic semiconductor film according to any one of <16> to <19>, which is formed by a solution coating method.
本発明によれば、移動度のバラツキが少なく、高温によるアニール処理を行わなくても高移動度である有機半導体素子及びその製造方法を提供することができる。
また、本発明によれば、有機半導体として好適な新規な化合物を提供することができる。
更に、本発明によれば、移動度のバラツキが少なく、高温によるアニール処理を行わなくても高移動度である有機半導体膜、及び、上記有機半導体膜を好適に形成することができる有機半導体膜形成用組成物を提供することができる。According to the present invention, it is possible to provide an organic semiconductor element having a low mobility variation and a high mobility without performing an annealing process at a high temperature, and a method for manufacturing the same.
Moreover, according to this invention, the novel compound suitable as an organic semiconductor can be provided.
Furthermore, according to the present invention, there is little variation in mobility, and the organic semiconductor film has a high mobility without performing an annealing process at a high temperature, and the organic semiconductor film that can suitably form the organic semiconductor film. A forming composition can be provided.
以下において、本発明の内容について詳細に説明する。以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。なお、本願明細書において「〜」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。また、本発明における有機EL素子とは、有機エレクトロルミネッセンス素子のことをいう。
本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有さないものとともに置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
また、本明細書における化学構造式は、水素原子を省略した簡略構造式で記載する場合もある。
また、本発明において、「質量%」と「重量%」とは同義であり、「質量部」と「重量部」とは同義である。
また、本発明において、好ましい態様の組み合わせは、より好ましい。Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the specification of the present application, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present invention, a combination of preferred embodiments is more preferred.
(有機半導体素子)
本発明の有機半導体素子は、式1で表される繰り返し単位を有する有機半導体(以下、「特定有機半導体化合物」ともいう。)を含有する有機半導体層を有することを特徴とする。(Organic semiconductor device)
The organic semiconductor element of the present invention includes an organic semiconductor layer containing an organic semiconductor having a repeating unit represented by Formula 1 (hereinafter also referred to as “specific organic semiconductor compound”).
本発明者は鋭意検討を重ねた結果、上記特定有機半導体化合物を含有することにより、得られる有機半導体素子や有機半導体膜の移動度のバラツキが少なく、高温によるアニール処理を行わなくても高移動度であることを見いだし、本発明を完成するに至ったものである。
詳細な効果の発現機構については不明であるが、上記特定有機半導体化合物は、膜質が均一となるため、移動度のバラツキが抑えられると考えられる。As a result of intensive studies, the present inventors have found that there is little variation in mobility of the obtained organic semiconductor element and organic semiconductor film by containing the specific organic semiconductor compound, and high mobility without performing annealing treatment at a high temperature. As a result, the present invention has been completed.
Although the mechanism of expression of the detailed effect is unknown, it is considered that the specific organic semiconductor compound has a uniform film quality, and thus variation in mobility can be suppressed.
<特定有機半導体化合物>
本発明において、特定有機半導体化合物は、下記式1で表される繰り返し単位を有する。<Specific organic semiconductor compound>
In the present invention, the specific organic semiconductor compound has a repeating unit represented by the following formula 1.
式1中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、O、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、Y11及びY12が同時にOとなることはなく、R11は一価の有機基を表し、Ar11、Ar12、Ar13はそれぞれ独立に、芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m11は0〜2の整数を表し、m12は0〜4の整数を表し、m13は0〜2の整数を表す。In Formula 1, X represents any of CR 12 2 , O, S, Se, NR 12 , SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents O, S, N-CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13. R 13 represents a monovalent organic group, a plurality of R 13 may be bonded to each other to form a ring, and Y 11 and Y 12 do not simultaneously become O, and R 11 is a monovalent group. Ar 11 , Ar 12 and Ar 13 each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, and m11 represents an integer of 0 to 2. , M12 represents an integer of 0 to 4, and m13 represents an integer of 0 to 2.
本発明の特定有機半導体化合物は、新規な化合物である。
また、本発明の特定有機半導体化合物は、有機半導体素子、有機半導体膜、及び、有機半導体膜形成用組成物に好適に用いることができる。The specific organic semiconductor compound of the present invention is a novel compound.
Moreover, the specific organic semiconductor compound of this invention can be used suitably for an organic semiconductor element, an organic semiconductor film, and the composition for organic-semiconductor film formation.
式1中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、O、S、NR12のいずれかであることがより好ましく、Sであることが更に好ましい。
R12はそれぞれ独立に、水素原子又は一価の有機基を表し、アルキル基が好ましく、炭素数1〜30のアルキル基がより好ましく、炭素数1〜15のアルキル基が更に好ましい。上記アルキル基は、直鎖状、分岐鎖状又は環状のいずれであってもよい。In Formula 1, X represents any one of CR 12 2 , O, S, Se, NR 12 , and SiR 12 2 , more preferably any of O, S, and NR 12 , and more preferably S. preferable.
R 12 each independently represents a hydrogen atom or a monovalent organic group, preferably an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, and still more preferably an alkyl group having 1 to 15 carbon atoms. The alkyl group may be linear, branched or cyclic.
Y11及びY12はそれぞれ独立に、O、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、Y11及びY12がいずれもSであるか、いずれもC(CN)2であることが好ましく、いずれもSであることがより好ましい。
Y11及びY12は異なっていてもよいが、製造適正の観点からは、同じであることが好ましい。
R13は一価の有機基を表し、アルキル基又はアリール基が好ましく、炭素数1〜10のアルキル基、又は、炭素数6〜10のアリール基がより好ましく、炭素数1〜10のアルキル基が更に好ましい。
複数のR13は互いに結合して環を形成してもよい。複数のR13により形成された環は、更にベンゼン環等の芳香環と縮環していてもよい。
また、Y11及びY12が同時にOとなることはない。Y 11 and Y 12 each independently represent O, S, N—CN, or CQ 2 , where Q is CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13 is represented, and both Y 11 and Y 12 are preferably S, or both are preferably C (CN) 2 , more preferably S.
Y 11 and Y 12 may be different, but are preferably the same from the viewpoint of production suitability.
R 13 represents a monovalent organic group, preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. Is more preferable.
A plurality of R 13 may be bonded to each other to form a ring. The ring formed by a plurality of R 13 may be further condensed with an aromatic ring such as a benzene ring.
Further, Y 11 and Y 12 do not become O at the same time.
R11は一価の有機基を表し、アルキル基、アリール基又はヘテロアリール基が好ましく、炭素数1〜40のアルキル基、炭素数6〜30のアリール基、炭素数4〜20のヘテロアリール基がより好ましく、炭素数1〜40のアルキル基が更に好ましく、炭素数1〜30のアルキル基が特に好ましい。
また、R11は、N原子との結合位置にビニレン基、又は、エチニレン基を有していてもよい。
アルキル基は、直鎖状、分岐鎖状又は環状のいずれであってもよい。
アリール基としては、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。
上記ヘテロアリール基としては、チオフェン環、ピロール環、チアゾール環、イミダゾール環、フラン環、ベンゾチオフェン環、ベンゾチアゾール環、及び、ベンゾイミダゾール環よりなる群から選ばれた環から1つの水素原子を除いた基が挙げられ、チオフェン環が好ましい。
上記アルキル基、アリール基及びヘテロアリール基は置換基を有していてもよい。好ましい置換基としては、アルキル基、アリール基、ポリシロキサンから1つの水素原子を除いた基が挙げられ、炭素数1〜8のアルキル基が好ましい。アリール基としてはフェニル基が好ましい。ポリシロキサンとしては、ジメチルポリシロキサンが好ましく、Si原子数が3〜8のジメチルポリシロキサンが好ましい。R 11 represents a monovalent organic group, preferably an alkyl group, an aryl group or a heteroaryl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 4 to 20 carbon atoms. Is more preferable, a C1-C40 alkyl group is still more preferable, and a C1-C30 alkyl group is especially preferable.
R 11 may have a vinylene group or an ethynylene group at the bonding position with the N atom.
The alkyl group may be linear, branched or cyclic.
As the aryl group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
As the heteroaryl group, one hydrogen atom is removed from a ring selected from the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring. A thiophene ring is preferred.
The alkyl group, aryl group and heteroaryl group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and groups obtained by removing one hydrogen atom from polysiloxane, and alkyl groups having 1 to 8 carbon atoms are preferred. The aryl group is preferably a phenyl group. As the polysiloxane, dimethylpolysiloxane is preferable, and dimethylpolysiloxane having 3 to 8 Si atoms is preferable.
Ar11、Ar12、Ar13はそれぞれ独立に、芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表す。
Ar11及びAr13は、芳香族炭化水素基、又は、芳香族複素環基であることが好ましく、多環構造を有していてもよいが、単環構造であることが好ましい。
芳香族炭化水素基としては、炭素数6〜20のアリーレン基が好ましく、フェニレン基又はナフチレン基が好ましく、フェニレン基がより好ましい。
芳香族複素環の複素原子としては特に限定されないが、S、O、N、Seが例示され、芳香族複素環基としては、チオフェン環、フラン環、ピラン環、ピロール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、セレノフェン環、イミダゾール環、及び、チエノチオフェン環よりなる群から選ばれた環から2つの水素原子を除いた基が挙げられ、チオフェン環、フラン環、ピロール環、ピリジン環、セレノフェン環、及び、チエノチオフェン環よりなる群から選ばれた環から2つの水素原子を除いた基が好ましく、チオフェン環から2つの水素原子を除いた基がより好ましい。
また、芳香族炭化水素基又は芳香族複素環基は置換基を有していてもよい。好ましい置換基としては、アルキル基が挙げられ、炭素数1〜20のアルキル基が好ましく、炭素数8〜20のアルキル基がより好ましい。
製造適性の観点から、Ar11とAr13は同一であることが好ましい。Ar 11 , Ar 12 and Ar 13 each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group.
Ar 11 and Ar 13 are preferably an aromatic hydrocarbon group or an aromatic heterocyclic group, and may have a polycyclic structure, but preferably a monocyclic structure.
As an aromatic hydrocarbon group, a C6-C20 arylene group is preferable, a phenylene group or a naphthylene group is preferable, and a phenylene group is more preferable.
Although it does not specifically limit as a hetero atom of an aromatic heterocyclic ring, S, O, N, and Se are illustrated, As an aromatic heterocyclic group, a thiophen ring, a furan ring, a pyran ring, a pyrrole ring, a pyridine ring, a pyrazine ring , A pyrimidine ring, a pyridazine ring, a selenophene ring, an imidazole ring, and a group obtained by removing two hydrogen atoms from a ring selected from the group consisting of thienothiophene rings, thiophene ring, furan ring, pyrrole ring, pyridine ring And a group obtained by removing two hydrogen atoms from a ring selected from the group consisting of a selenophene ring and a thienothiophene ring, and a group obtained by removing two hydrogen atoms from a thiophene ring is more preferred.
Moreover, the aromatic hydrocarbon group or the aromatic heterocyclic group may have a substituent. Preferable substituents include an alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 8 to 20 carbon atoms is more preferable.
From the viewpoint of production suitability, Ar 11 and Ar 13 are preferably the same.
Ar12は、芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、縮合多環芳香族基、ビニレン基、又は、チエニレン基を表すことが好ましい。
芳香族炭化水素基としては、炭素数6〜20のアリーレン基が好ましく、フェニレン基、ナフチレン基、又は、アントラセン環から2つの水素原子を除いた基が好ましい。
芳香族複素環の複素原子としては特に限定されないが、S、O、N、Seが例示され、芳香族複素環基としては、チオフェン環、フラン環、ピラン環、ピロール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、セレノフェン環、イミダゾール環、及び、チエノチオフェン環よりなる群から選ばれた環から2つの水素原子を除いた基が挙げられ、チオフェン環、フラン環、ピロール環、ピリジン環、セレノフェン環、及び、チエノチオフェン環よりなる群から選ばれた環から2つの水素原子を除いた基が好ましく、チオフェン環、及び、チエノチオフェン環よりなる群から選ばれた環から2つの水素原子を除いた基がより好ましく、チオフェン環から2つの水素原子を除いた基が更に好ましい。
上記芳香族炭化水素基又は芳香族複素環基は置換基を有していてもよい。好ましい置換基としては、アルキル基が挙げられ、炭素数1〜20のアルキル基が好ましく、炭素数8〜20のアルキル基がより好ましい。
また、Ar12は、複数の芳香族炭化水素基や芳香族複素環基が縮環した縮合多環芳香族基を表すことが好ましい。Ar12が縮合多環芳香族基を表す場合、3〜7環の縮環であることが好ましく、3〜5環の縮環であることが好ましい。上記縮環中には、シクロテトラメチレンシラン等の非芳香族複素環基を含んでもよい。
また、Ar12が縮合多環芳香族基を表す場合、下記式AR−1〜AR−10のいずれかで表される構造であることが好ましい。Ar 12 represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group, or an ethynylene group, and preferably represents a condensed polycyclic aromatic group, a vinylene group, or a thienylene group.
As the aromatic hydrocarbon group, an arylene group having 6 to 20 carbon atoms is preferable, and a phenylene group, a naphthylene group, or a group in which two hydrogen atoms are removed from an anthracene ring is preferable.
Although it does not specifically limit as a hetero atom of an aromatic heterocyclic ring, S, O, N, and Se are illustrated, As an aromatic heterocyclic group, a thiophen ring, a furan ring, a pyran ring, a pyrrole ring, a pyridine ring, a pyrazine ring , A pyrimidine ring, a pyridazine ring, a selenophene ring, an imidazole ring, and a group obtained by removing two hydrogen atoms from a ring selected from the group consisting of thienothiophene rings, thiophene ring, furan ring, pyrrole ring, pyridine ring A group obtained by removing two hydrogen atoms from a ring selected from the group consisting of a selenophene ring and a thienothiophene ring, and two hydrogen atoms from a ring selected from the group consisting of a thiophene ring and a thienothiophene ring Is more preferable, and a group in which two hydrogen atoms are removed from the thiophene ring is more preferable.
The aromatic hydrocarbon group or aromatic heterocyclic group may have a substituent. Preferable substituents include an alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 8 to 20 carbon atoms is more preferable.
Ar 12 preferably represents a condensed polycyclic aromatic group in which a plurality of aromatic hydrocarbon groups or aromatic heterocyclic groups are condensed. When Ar 12 represents a condensed polycyclic aromatic group, it is preferably a 3-7 ring condensed ring, and more preferably a 3-5 ring condensed ring. The condensed ring may contain a non-aromatic heterocyclic group such as cyclotetramethylene silane.
Also, if the Ar 12 represents a fused polycyclic aromatic group, preferably a structure represented by any one of the following formulas AR-1~AR-10.
式AR−1〜式AR−10中、XA1、XA2、XA4、及び、XA5はそれぞれ独立に、S、O、CRAR 2、NRAR、SiRAR 2のいずれかを表し、RARはそれぞれ独立に、一価の有機基を表す。RARは炭素数8〜20のアルキル基であることが好ましい。
これらの中で、AR−1〜AR−6、AR−9、又はAR−10であることが好ましく、AR−1〜AR−5のいずれかであることがより好ましく、AR−1又はAR−5であることが更に好ましい。
また、上記多環の芳香族炭化水素基又は多環の芳香族複素環基は置換基を有していてもよい。好ましい置換基としては、アルキル基が挙げられ、炭素数1〜30のアルキル基が好ましく、炭素数8〜20のアルキル基がより好ましい。In Formula AR-1 to Formula AR-10, X A1 , X A2 , X A4 , and X A5 each independently represent any of S, O, CR AR 2 , NR AR , SiR AR 2 , and R Each AR independently represents a monovalent organic group. R AR is preferably an alkyl group having 8 to 20 carbon atoms.
Among these, AR-1 to AR-6, AR-9, or AR-10 is preferable, and any of AR-1 to AR-5 is more preferable, and AR-1 or AR- More preferably, it is 5.
The polycyclic aromatic hydrocarbon group or the polycyclic aromatic heterocyclic group may have a substituent. Preferable substituents include an alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable, and an alkyl group having 8 to 20 carbon atoms is more preferable.
m11は0〜2の整数を表し、m12は0〜4の整数を表し、m13は0〜2の整数を表し、m11とm12とm13の合計が1以上であることが好ましい。
Ar12がビニレン基又はエチニレン基である場合、m12は1であることが好ましく、m11及びm13はそれぞれ独立に、1又は2であることが好ましい。
Ar12が芳香族炭化水素基、又は、芳香族複素環基である場合、m12は1又は2であることが好ましく、m11及びm13はそれぞれ独立に、0又は1であることが好ましい。
Ar12が縮合多環芳香族基である場合、m12は1であることが好ましく、m11及びm13はそれぞれ独立に、0又は1であることが好ましい。m11 represents an integer of 0 to 2, m12 represents an integer of 0 to 4, m13 represents an integer of 0 to 2, and the total of m11, m12, and m13 is preferably 1 or more.
When Ar 12 is a vinylene group or an ethynylene group, m12 is preferably 1, and m11 and m13 are each independently preferably 1 or 2.
When Ar 12 is an aromatic hydrocarbon group or an aromatic heterocyclic group, m12 is preferably 1 or 2, and m11 and m13 are each independently preferably 0 or 1.
When Ar 12 is a condensed polycyclic aromatic group, m12 is preferably 1, and m11 and m13 are each independently preferably 0 or 1.
また、式1で表される繰り返し単位は、式2で表される繰り返し単位であることが好ましい。 Moreover, it is preferable that the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.
式2中、X、Y11、Y12、R11、Ar12、及び、m12は、それぞれ式1中のX、Y11、Y12、R11、Ar12、及び、m12と同義であり、好ましい範囲も同様であり、X21及びX22はそれぞれ独立に、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、R21〜R24はそれぞれ独立に、水素原子又は一価の有機基を表し、m11’は0〜2の整数を表し、m13’は0〜2の整数を表す。In the formula 2, X, Y 11, Y 12, R 11, Ar 12 and, m12 is, X in each formula 1, Y 11, Y 12, R 11, Ar 12, and is synonymous with m12, The preferred ranges are also the same. X 21 and X 22 each independently represents any of O, S, Se, NR 12 , and SiR 12 2 , and R 12 each independently represents a hydrogen atom or a monovalent organic group. R 21 to R 24 each independently represents a hydrogen atom or a monovalent organic group, m 11 ′ represents an integer of 0 to 2, and m 13 ′ represents an integer of 0 to 2.
X21及びX22はそれぞれ独立に、O、S、Se、NR12’、SiR12’ 2のいずれかを表し、O、S、NR12’のいずれかであることがより好ましく、Sであることが更に好ましい。
R12’はそれぞれ独立に、水素原子又は一価の有機基を表し、アルキル基が好ましく、炭素数1〜30のアルキル基がより好ましく、炭素数1〜15のアルキル基が更に好ましい。上記アルキル基は、直鎖状、分岐鎖状又は環状のいずれであってもよい。
R21〜R24はそれぞれ独立に、水素原子又は一価の有機基を表し、炭素数1〜20のアルキル基が好ましく、炭素数8〜20のアルキル基がより好ましい。
m11’は0〜2の整数を表し、m13’は0〜2の整数を表し、m11’とm12とm13’の合計が1以上であることが好ましい。
Ar12がビニレン基又はエチニレン基である場合、m12は1を表し、m11’及びm13’はそれぞれ独立に、1又は2であることが好ましい。
Ar12が芳香族炭化水素基、又は、芳香族複素環基である場合、m12は1又は2であることが好ましく、m11’及びm13’はそれぞれ独立に、0又は1であることが好ましい。
Ar12が縮合多環芳香族基である場合、m12は1であることが好ましく、m11’及びm13’はそれぞれ独立に、0又は1であることが好ましい。X 21 and X 22 each independently represent any of O, S, Se, NR 12 ′ , and SiR 12 ′ 2 , more preferably any of O, S, and NR 12 ′ , and S. More preferably.
R 12 ′ each independently represents a hydrogen atom or a monovalent organic group, preferably an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, and still more preferably an alkyl group having 1 to 15 carbon atoms. The alkyl group may be linear, branched or cyclic.
R 21 to R 24 each independently represents a hydrogen atom or a monovalent organic group, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 8 to 20 carbon atoms.
m11 ′ represents an integer of 0 to 2, m13 ′ represents an integer of 0 to 2, and the total of m11 ′, m12, and m13 ′ is preferably 1 or more.
When Ar 12 is a vinylene group or an ethynylene group, m12 represents 1, and m11 ′ and m13 ′ are preferably each independently 1 or 2.
When Ar 12 is an aromatic hydrocarbon group or an aromatic heterocyclic group, m12 is preferably 1 or 2, and m11 ′ and m13 ′ are each independently preferably 0 or 1.
When Ar 12 is a condensed polycyclic aromatic group, m12 is preferably 1, and m11 ′ and m13 ′ are each independently preferably 0 or 1.
特定有機半導体化合物中、式1で表される繰り返し単位の含有量は、特定有機半導体化合物の全質量に対し、60〜100質量%であることが好ましく、80〜100質量%であることがより好ましく、90〜100質量%であることが更に好ましい。 In the specific organic semiconductor compound, the content of the repeating unit represented by Formula 1 is preferably 60 to 100% by mass and more preferably 80 to 100% by mass with respect to the total mass of the specific organic semiconductor compound. Preferably, it is 90-100 mass%.
特定有機半導体化合物の重量平均分子量は、特に制限されないが、1,000〜200万が好ましく、10,000〜100万がより好ましく、50,000〜50万が更に好ましい。
分子量を上記範囲内とすることにより、溶媒への溶解性と薄膜の膜質安定性とを両立することができる。
本発明において、重量平均分子量及び数平均分子量は、ゲル浸透クロマトグラフィ法(GPC)法にて測定され、標準ポリスチレンで換算して求められる。具体的には、例えば、GPCは、HLC−8220GPC(東ソー(株)製)を用い、カラムとして、TSKgeL SuperHZM−H、TSKgeL SuperHZ4000、TSKgeL SuperHZ2000(東ソー(株)製、4.6mmID×15cm)を3本用い、溶離液としてTHF(テトラヒドロフラン)を用いる。また、条件としては、試料濃度を0.35質量%、流速を0.35ml/min、サンプル注入量を10μl、測定温度を40℃とし、IR検出器を用いて行う。また、検量線は、東ソー(株)製「標準試料TSK
standard,polystyrene」:「F−40」、「F−20」、「F−4」、「F−1」、「A−5000」、「A−2500」、「A−1000」、「n−プロピルベンゼン」の8サンプルから作製する。
後述する有機半導体層、後述する有機半導体膜又は有機半導体膜形成用組成物中には、1種のみの特定有機半導体化合物が含まれていても、2種以上の特定有機半導体化合物が含まれていてもよいが、配向性の観点から、1種のみであることが好ましい。The weight average molecular weight of the specific organic semiconductor compound is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 10,000 to 1,000,000, and still more preferably 50,000 to 500,000.
By setting the molecular weight within the above range, both solubility in a solvent and film quality stability of the thin film can be achieved.
In the present invention, the weight average molecular weight and the number average molecular weight are measured by a gel permeation chromatography method (GPC) method and are calculated by standard polystyrene. Specifically, for example, GPC uses HLC-8220GPC (manufactured by Tosoh Corporation), and TSKgeL SuperHZM-H, TSKgeL SuperHZ4000, TSKgeL SuperHZ2000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation) are used as columns. Three are used and THF (tetrahydrofuran) is used as an eluent. As conditions, the sample concentration is 0.35% by mass, the flow rate is 0.35 ml / min, the sample injection amount is 10 μl, the measurement temperature is 40 ° C., and an IR detector is used. The calibration curve is “Standard sample TSK” manufactured by Tosoh Corporation.
“standard, polystyrene”: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-2500”, “A-1000”, “n-” Prepared from 8 samples of “propylbenzene”.
The organic semiconductor layer described later, the organic semiconductor film described later, or the composition for forming an organic semiconductor film includes two or more specific organic semiconductor compounds even if only one specific organic semiconductor compound is included. However, from the viewpoint of orientation, only one type is preferable.
本発明に用いられる式1で表される特定有機半導体化合物の具体例としては、下記に示す繰り返し単位を含有する化合物(E−1〜E−26)が好ましく例示されるが、本発明はこれらの例に限定されるものではない。 As specific examples of the specific organic semiconductor compound represented by Formula 1 used in the present invention, compounds (E-1 to E-26) containing the repeating units shown below are preferably exemplified. It is not limited to the example.
これらの中でも、E−1、E−3、E−4、E−5、及びE−8が好ましく、E−1、E−4、及びE−5がより好ましい。 Among these, E-1, E-3, E-4, E-5, and E-8 are preferable, and E-1, E-4, and E-5 are more preferable.
特定有機半導体化合物の合成方法は、特に制限されず、公知の方法を参照して合成できる。例えば、特開2011−168747号公報、Macromol.,2013,46,3887.及びJ.Org.Chem.1985,50,1681.等を参考に合成することができる。 The method for synthesizing the specific organic semiconductor compound is not particularly limited, and can be synthesized with reference to known methods. For example, JP 2011-168747 A, Macromol. , 2013, 46, 3887. And J.A. Org. Chem. 1985, 50, 1681. Etc. can be synthesized with reference to the above.
本発明の有機半導体素子の有機半導体層又は後述する本発明の有機半導体膜における、特定有機半導体化合物の含有量は、有機半導体層又は有機半導体膜の全質量に対し、30〜100質量%であることが好ましく、50〜100質量%であることがより好ましく、70〜100質量%であることが更に好ましい。また、後述するバインダーポリマーを含有しない場合は、上記含有量が、有機半導体層又は有機半導体膜の全質量に対し、90〜100質量%であることが好ましく、95〜100質量%であることがより好ましい。 The content of the specific organic semiconductor compound in the organic semiconductor layer of the organic semiconductor element of the present invention or the organic semiconductor film of the present invention described later is 30 to 100% by mass with respect to the total mass of the organic semiconductor layer or the organic semiconductor film. It is preferable that it is 50-100 mass%, It is more preferable that it is 70-100 mass%. Moreover, when not containing the binder polymer mentioned later, it is preferable that the said content is 90-100 mass% with respect to the total mass of an organic-semiconductor layer or an organic-semiconductor film, and it is 95-100 mass%. More preferred.
(化合物)
本発明の化合物は、式1で表される繰り返し単位を有する。(Compound)
The compound of the present invention has a repeating unit represented by Formula 1.
式1中、X、Y11、Y12、R11、Ar11、Ar12、Ar13、m11、m12、及び、m13はそれぞれ、特定有機半導体化合物におけるX、Y11、Y12、R11、Ar11、Ar12、Ar13、m11、m12、及び、m13と同義であり、好ましい態様も同様である。In Formula 1, X, Y 11 , Y 12 , R 11 , Ar 11 , Ar 12 , Ar 13 , m11, m12, and m13 are X, Y 11 , Y 12 , R 11 , and R 13 in the specific organic semiconductor compound, respectively. Ar 11, Ar 12, Ar 13 , m11, m12, and have the same meanings as m13, preferable embodiments thereof are also the same.
本発明の化合物は有機半導体化合物であることが好ましい。
また、本発明の化合物中の式1で表される繰り返し単位の含有量、重量平均分子量、具体例及び合成方法は、特定有機半導体化合物におけるそれらと同義であり、好ましい態様も同様である。The compound of the present invention is preferably an organic semiconductor compound.
In addition, the content, weight average molecular weight, specific examples and synthesis method of the repeating unit represented by Formula 1 in the compound of the present invention are the same as those in the specific organic semiconductor compound, and the preferred embodiments are also the same.
<バインダーポリマー>
本発明の有機半導体素子の有機半導体層は、バインダーポリマーを含有することが好ましい。
また、本発明の有機半導体素子は、上記有機半導体層とバインダーポリマーを含む層を有する有機半導体素子であってもよい。
バインダーポリマーの種類は特に制限されず、公知のバインダーポリマーを用いることができる。
バインダーポリマーとしては、ポリスチレン、ポリカーボネート、ポリアリレート、ポリエステル、ポリアミド、ポリイミド、ポリウレタン、ポリシロキサン、ポリスルフォン、ポリメチルメタクリレート、ポリメチルアクリレート、セルロース、ポリエチレン、ポリプロピレンなどの絶縁性ポリマー、及びこれらの共重合体、ポリシラン、ポリカルバゾール、ポリアリールアミン、ポリフルオレン、ポリチオフェン、ポリピロール、ポリアニリン、ポリパラフェニレンビニレン、ポリアセン、ポリヘテロアセンなどの半導体ポリマー、及びこれらの共重合体、ゴム、熱可塑性エラストマーを挙げることができる。
中でも、バインダーポリマーとしては、ベンゼン環を有する高分子化合物(ベンゼン環基を有する単量体単位を有する高分子)が好ましい。ベンゼン環基を有する単量体単位の含有量は特に制限されないが、全単量体単位中、50モル%以上が好ましく、70モル%以上がより好ましく、90モル%以上が更に好ましい。上限は特に制限されないが、100モル%が挙げられる。
上記バインダーポリマーとしては、例えば、ポリスチレン、ポリ(α−メチルスチレン)、ポリビニルシンナメート、ポリ(4−ビニルフェニル)、ポリ(4−メチルスチレン)、ポリ[ビス(4−フェニル)(2,4,6−トリメチルフェニル)アミン]、ポリ[2,6−(4,4−ビス(2−エチルヘキシル)−4Hシクロペンタ[2,1−b;3,4−b’]ジチオフェン)−アルト−4,7−(2,1,3−ベンゾチアジアゾール)]などが挙げられ、ポリ(α−メチルスチレン)が特に好ましい。<Binder polymer>
The organic semiconductor layer of the organic semiconductor element of the present invention preferably contains a binder polymer.
The organic semiconductor element of the present invention may be an organic semiconductor element having the organic semiconductor layer and a layer containing a binder polymer.
The kind in particular of a binder polymer is not restrict | limited, A well-known binder polymer can be used.
Binder polymers include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, polypropylene, and their co-polymers. Mention of semiconducting polymers such as coalescence, polysilane, polycarbazole, polyarylamine, polyfluorene, polythiophene, polypyrrole, polyaniline, polyparaphenylenevinylene, polyacene, polyheteroacene, and their copolymers, rubber, thermoplastic elastomers Can do.
Among these, as the binder polymer, a polymer compound having a benzene ring (a polymer having a monomer unit having a benzene ring group) is preferable. The content of the monomer unit having a benzene ring group is not particularly limited, but is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more in all monomer units. The upper limit is not particularly limited, but 100 mol% can be mentioned.
Examples of the binder polymer include polystyrene, poly (α-methylstyrene), polyvinyl cinnamate, poly (4-vinylphenyl), poly (4-methylstyrene), and poly [bis (4-phenyl) (2,4 , 6-trimethylphenyl) amine], poly [2,6- (4,4-bis (2-ethylhexyl) -4Hcyclopenta [2,1-b; 3,4-b ′] dithiophene) -alt-4, 7- (2,1,3-benzothiadiazole)] and the like, and poly (α-methylstyrene) is particularly preferable.
バインダーポリマーの重量平均分子量は、特に制限されないが、1,000〜200万が好ましく、3,000〜100万がより好ましく、5,000〜60万が更に好ましい。
また、後述する溶媒を用いる場合、バインダーポリマーは、使用する溶媒への溶解度が、特定有機半導体化合物よりも高いことが好ましい。上記態様であると、得られる有機半導体の移動度及び熱安定性により優れる。
本発明の有機半導体素子の有機半導体層におけるバインダーポリマーの含有量は、特定有機半導体化合物の含有量100質量部に対し、1〜200質量部であることが好ましく、10〜150質量部であることがより好ましく、20〜120質量部であることが更に好ましい。上記範囲であると、得られる有機半導体の移動度及び熱安定性により優れる。The weight average molecular weight of the binder polymer is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 3,000 to 1,000,000, and still more preferably 5,000 to 600,000.
Moreover, when using the solvent mentioned later, it is preferable that the binder polymer has higher solubility in the solvent used than the specific organic semiconductor compound. It is excellent in the mobility and thermal stability of the organic semiconductor obtained as it is the said aspect.
It is preferable that content of the binder polymer in the organic-semiconductor layer of the organic-semiconductor element of this invention is 1-200 mass parts with respect to 100 mass parts of content of a specific organic semiconductor compound, It is 10-150 mass parts. Is more preferable, and it is still more preferable that it is 20-120 mass parts. It is excellent in the mobility and thermal stability of the organic semiconductor obtained as it is the said range.
<その他の成分>
本発明の有機半導体素子における有機半導体層には、特定有機半導体化合物及びバインダーポリマー以外に他の成分が含まれていてもよい。
その他の成分としては、公知の添加剤等を用いることができる。
上記有機半導体層における特定有機半導体化合物及びバインダーポリマー以外の成分の含有量は、有機半導体層の全質量に対し、10質量%以下であることが好ましく、5質量%以下であることが好ましく、1質量%以下であることが更に好ましく、0.1質量%以下であることが特に好ましい。上記範囲であると、膜形成性に優れ、得られる有機半導体の移動度及び熱安定性により優れる。<Other ingredients>
The organic semiconductor layer in the organic semiconductor element of the present invention may contain other components in addition to the specific organic semiconductor compound and the binder polymer.
As other components, known additives and the like can be used.
The content of the components other than the specific organic semiconductor compound and the binder polymer in the organic semiconductor layer is preferably 10% by mass or less, and preferably 5% by mass or less, based on the total mass of the organic semiconductor layer. It is more preferable that the amount is not more than mass%, and it is particularly preferable that it is not more than 0.1% by mass. When it is in the above range, the film-forming property is excellent, and the mobility and thermal stability of the obtained organic semiconductor are excellent.
本発明の有機半導体素子における有機半導体層の形成方法は特に制限されず、後述する本発明の有機半導体膜形成用組成物を、ソース電極、ドレイン電極、及び、ゲート絶縁膜上に付与して、必要に応じて乾燥処理を施すことにより、所望の有機半導体層を形成することができる。 The method for forming the organic semiconductor layer in the organic semiconductor element of the present invention is not particularly limited, and a composition for forming an organic semiconductor film of the present invention described later is applied on the source electrode, the drain electrode, and the gate insulating film, A desired organic semiconductor layer can be formed by performing a drying treatment as necessary.
本発明の有機半導体素子は、後述する本発明の有機半導体膜形成用組成物を用いて製造されたものであることが好ましい。
本発明の有機半導体膜形成用組成物を用いて有機半導体膜や有機半導体素子を製造する方法は、特に制限されず、公知の方法を採用できる。例えば、組成物を所定の基材上に付与して、必要に応じて乾燥処理を施して、有機半導体膜を製造する方法(「溶液塗布法」ともいう。)が挙げられる。
基材上に組成物を付与する方法は特に制限されず、公知の方法を採用でき、例えば、インクジェット印刷法、フレキソ印刷法、バーコート法、スピンコート法、ナイフコート法、ドクターブレード法などが挙げられ、インクジェット印刷法、フレキソ印刷法が好ましい。
なお、フレキソ印刷法としては、フレキソ印刷版として感光性樹脂版を用いる態様が好適に挙げられる。態様によって、組成物を基板上に印刷して、パターンを容易に形成することができる。
中でも、本発明の有機半導体素子の製造方法は、本発明の有機半導体膜形成用組成物を基板上に塗布する塗布工程、を含むことが好ましく、本発明の有機半導体膜形成用組成物が溶媒を含み、本発明の有機半導体膜形成用組成物を基板上に塗布する塗布工程、及び、塗布された組成物から溶媒を除去する除去工程を含むことがより好ましい。The organic semiconductor element of the present invention is preferably manufactured using the composition for forming an organic semiconductor film of the present invention described later.
A method for producing an organic semiconductor film or an organic semiconductor element using the composition for forming an organic semiconductor film of the present invention is not particularly limited, and a known method can be adopted. For example, there is a method (also referred to as “solution coating method”) in which an organic semiconductor film is manufactured by applying the composition onto a predetermined substrate and performing a drying treatment as necessary.
The method for applying the composition on the substrate is not particularly limited, and a known method can be adopted, for example, an inkjet printing method, a flexographic printing method, a bar coating method, a spin coating method, a knife coating method, a doctor blade method, or the like. The inkjet printing method and the flexographic printing method are preferable.
In addition, as a flexographic printing method, the aspect using a photosensitive resin plate as a flexographic printing plate is mentioned suitably. In some embodiments, the composition can be printed on a substrate to easily form a pattern.
Especially, it is preferable that the manufacturing method of the organic-semiconductor element of this invention includes the application | coating process which apply | coats the composition for organic-semiconductor film formation of this invention on a board | substrate, The composition for organic-semiconductor film formation of this invention is a solvent. It is more preferable to include a coating step for coating the composition for forming an organic semiconductor film of the present invention on a substrate and a removing step for removing the solvent from the coated composition.
後述する本発明の有機半導体膜形成用組成物は、溶媒を含むことが好ましく、有機溶媒を含むことがより好ましい。
溶媒としては、公知の溶媒を用いることができる。
具体的には、例えば、ヘキサン、オクタン、デカン、トルエン、キシレン、メシチレン、エチルベンゼン、デカリン、1−メチルナフタレンなどの炭化水素系溶媒、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系溶媒、ジクロロメタン、クロロホルム、テトラクロロメタン、ジクロロエタン、トリクロロエタン、テトラクロロエタン、クロロベンゼン、ジクロロベンゼン、クロロトルエンなどのハロゲン化炭化水素系溶媒、酢酸エチル、酢酸ブチル、酢酸アミルなどのエステル系溶媒、メタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、メチルセロソルブ、エチルセロソルブ、エチレングリコールなどのアルコール系溶媒、ジブチルエーテル、テトラヒドロフラン、ジオキサン、アニソールなどのエーテル系溶媒、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド等のアミド系溶媒、1−メチル−2−ピロリドン、1−メチル−2−イミダゾリジノン等のイミド系溶媒、ジメチルスルフォキサイドなどのスルホキシド系溶媒、アセトニトリルなどのニトリル系溶媒が挙げられる。The composition for forming an organic semiconductor film of the present invention to be described later preferably contains a solvent, and more preferably contains an organic solvent.
A known solvent can be used as the solvent.
Specifically, for example, hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin, 1-methylnaphthalene, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, methanol, propanol, Alcohol solvents such as butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, dibutyl ether Ether solvents such as tetrahydrofuran, dioxane and anisole, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, imides such as 1-methyl-2-pyrrolidone and 1-methyl-2-imidazolidinone And nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethyl sulfoxide, and acetonitrile.
溶媒は、1種単独で用いてもよく、複数組み合わせて用いてもよい。
これらの中でも、炭化水素系溶媒、ハロゲン化炭化水素系溶媒、芳香族系溶媒、芳香族複素環系溶媒、及び/又はエーテル系溶媒が好ましく、トルエン、キシレン、メシチレン、テトラリン、ジクロロベンゼン又はアニソールがより好ましい。A solvent may be used individually by 1 type and may be used in combination of multiple.
Among these, hydrocarbon solvents, halogenated hydrocarbon solvents, aromatic solvents, aromatic heterocyclic solvents, and / or ether solvents are preferred, and toluene, xylene, mesitylene, tetralin, dichlorobenzene, or anisole are preferred. More preferred.
溶媒の沸点が100℃以上であることが、製膜性の観点から好ましい。溶媒の沸点は、100〜300℃であることがより好ましく、125〜250℃であることが更に好ましく、150〜225℃であることが特に好ましい。
なお、最も含有量の多い溶媒の沸点が100℃以上であることが好ましく、全ての溶媒の沸点が100℃以上であることがより好ましい。It is preferable from a viewpoint of film forming property that the boiling point of a solvent is 100 degreeC or more. The boiling point of the solvent is more preferably 100 to 300 ° C, further preferably 125 to 250 ° C, and particularly preferably 150 to 225 ° C.
In addition, it is preferable that the boiling point of the solvent with most content is 100 degreeC or more, and it is more preferable that the boiling points of all the solvents are 100 degreeC or more.
溶媒を含有する場合、本発明の有機半導体膜形成用組成物における特定有機半導体化合物の含有量は、有機半導体膜形成用組成物の全質量に対し、0.05〜50質量%であることが好ましく、0.1〜25質量%であることがより好ましく、0.25〜15質量%であることが更に好ましく、0.4〜10質量%であることが特に好ましく、また、バインダーポリマーの含有量は、有機半導体膜形成用組成物の全質量に対し、0.01〜50質量%であることが好ましく、0.05〜25質量%であることがより好ましく、0.1〜10質量%であることが更に好ましい。上記範囲であると、塗布性に優れ、容易に有機半導体膜を形成することができる。 When the solvent is contained, the content of the specific organic semiconductor compound in the composition for forming an organic semiconductor film of the present invention is 0.05 to 50% by mass with respect to the total mass of the composition for forming an organic semiconductor film. Preferably, it is 0.1 to 25% by mass, more preferably 0.25 to 15% by mass, particularly preferably 0.4 to 10% by mass, and inclusion of a binder polymer The amount is preferably 0.01 to 50% by mass, more preferably 0.05 to 25% by mass, and 0.1 to 10% by mass with respect to the total mass of the composition for forming an organic semiconductor film. More preferably. Within the above range, the coating property is excellent and the organic semiconductor film can be easily formed.
上記除去工程における乾燥処理は、必要に応じて実施される処理であり、使用される特定有機半導体化合物及び溶媒の種類により適宜最適な条件が選択される。中でも、得られる有機半導体の移動度及び熱安定性により優れ、また、生産性に優れる点で、加熱温度としては30℃〜100℃が好ましく、40℃〜80℃がより好ましく、加熱時間としては10〜300分が好ましく、30〜180分がより好ましい。 The drying process in the removal step is a process performed as necessary, and optimal conditions are appropriately selected depending on the type of the specific organic semiconductor compound and the solvent used. Among them, the heating temperature is preferably 30 ° C. to 100 ° C., more preferably 40 ° C. to 80 ° C., and the heating time is excellent in terms of mobility and thermal stability of the obtained organic semiconductor and excellent productivity. 10 to 300 minutes are preferable, and 30 to 180 minutes are more preferable.
形成される有機半導体層の厚さは、特に制限されないが、得られる有機半導体の移動度及び熱安定性の観点から、10〜500nmが好ましく、30〜200nmがより好ましい。 The thickness of the formed organic semiconductor layer is not particularly limited, but is preferably 10 to 500 nm, and more preferably 30 to 200 nm, from the viewpoint of the mobility and thermal stability of the obtained organic semiconductor.
有機半導体素子としては、特に制限はないが、2〜5端子の有機半導体素子であることが好ましく、2又は3端子の有機半導体素子であることがより好ましい。
また、有機半導体素子としては、光電変換素子でないことが好ましい。
更に、本発明の有機半導体素子は、非発光性有機半導体素子であることが好ましい。
2端子素子としては、整流用ダイオード、定電圧ダイオード、PINダイオード、ショットキーバリアダイオード、サージ保護用ダイオード、ダイアック、バリスタ、トンネルダイオード等が挙げられる。
3端子素子としては、バイポーラトランジスタ、ダーリントントランジスタ、電界効果トランジスタ、絶縁ゲートバイポーラトランジスタ、ユニジャンクショントランジスタ、静電誘導トランジスタ、ゲートターンサイリスタ、トライアック、静電誘導サイリスタ等が挙げられる。
これらの中でも、整流用ダイオード、及び、トランジスタ類が好ましく挙げられ、電界効果トランジスタがより好ましく挙げられる。Although there is no restriction | limiting in particular as an organic semiconductor element, It is preferable that it is a 2-5 terminal organic semiconductor element, and it is more preferable that it is a 2 or 3 terminal organic semiconductor element.
The organic semiconductor element is preferably not a photoelectric conversion element.
Furthermore, the organic semiconductor element of the present invention is preferably a non-light emitting organic semiconductor element.
Examples of the two-terminal element include a rectifying diode, a constant voltage diode, a PIN diode, a Schottky barrier diode, a surge protection diode, a diac, a varistor, and a tunnel diode.
Examples of the three-terminal element include a bipolar transistor, a Darlington transistor, a field effect transistor, an insulated gate bipolar transistor, a unijunction transistor, a static induction transistor, a gate turn thyristor, a triac, and a static induction thyristor.
Among these, a rectifying diode and transistors are preferably exemplified, and a field effect transistor is more preferably exemplified.
本発明の有機薄膜トランジスタの一態様について図面を参照して説明する。
図1は、本発明の有機半導体素子(有機薄膜トランジスタ(有機TFT))の一態様の断面模式図である。
図1において、有機薄膜トランジスタ100は、基板10と、基板10上に配置されたゲート電極20と、ゲート電極20を覆うゲート絶縁膜30と、ゲート絶縁膜30のゲート電極20側とは反対側の表面に接するソース電極40及びドレイン電極42と、ソース電極40とドレイン電極42との間のゲート絶縁膜30の表面を覆う有機半導体膜50と、各部材を覆う封止層60とを備える。有機薄膜トランジスタ100は、ボトムゲート−ボトムコンタクト型の有機薄膜トランジスタである。
なお、図1においては、有機半導体膜50が、上述した組成物より形成される膜に該当する。
以下、基板、ゲート電極、ゲート絶縁膜、ソース電極、ドレイン電極、有機半導体膜及び封止層並びにそれぞれの形成方法について詳述する。One embodiment of the organic thin film transistor of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of one embodiment of the organic semiconductor element (organic thin film transistor (organic TFT)) of the present invention.
In FIG. 1, an organic thin film transistor 100 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and a side of the gate insulating film 30 opposite to the gate electrode 20 side. A source electrode 40 and a drain electrode 42 in contact with the surface, an organic semiconductor film 50 covering the surface of the gate insulating film 30 between the source electrode 40 and the drain electrode 42, and a sealing layer 60 covering each member are provided. The organic thin film transistor 100 is a bottom gate-bottom contact type organic thin film transistor.
In FIG. 1, the organic semiconductor film 50 corresponds to a film formed from the above-described composition.
Hereinafter, the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, the sealing layer, and the respective formation methods will be described in detail.
<基板>
基板は、後述するゲート電極、ソース電極、ドレイン電極などを支持する役割を果たす。
基板の種類は特に制限されず、例えば、プラスチック基板、ガラス基板、セラミック基板などが挙げられる。中でも、各デバイスへの適用性及びコストの観点から、ガラス基板又はプラスチック基板であることが好ましい。
プラスチック基板の材料としては、熱硬化性樹脂(例えば、エポキシ樹脂、フェノール樹脂、ポリイミド樹脂、ポリエステル樹脂(例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)など)又は熱可塑性樹脂(例えば、フェノキシ樹脂、ポリエーテルスルフォン、ポリスルフォン、ポリフェニレンスルフォンなど)が挙げられる。
セラミック基板の材料としては、例えば、アルミナ、窒化アルミニウム、ジルコニア、シリコン、窒化シリコン、シリコンカーバイドなどが挙げられる。
ガラス基板の材料としては、例えば、ソーダガラス、カリガラス、ホウケイ酸ガラス、石英ガラス、アルミケイ酸ガラス、鉛ガラスなどが挙げられる。<Board>
The substrate plays a role of supporting a gate electrode, a source electrode, a drain electrode, and the like described later.
The kind of board | substrate is not restrict | limited in particular, For example, a plastic substrate, a glass substrate, a ceramic substrate etc. are mentioned. Among these, a glass substrate or a plastic substrate is preferable from the viewpoint of applicability to each device and cost.
The material of the plastic substrate may be a thermosetting resin (for example, epoxy resin, phenol resin, polyimide resin, polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN)) or thermoplastic resin (for example, phenoxy). Resin, polyether sulfone, polysulfone, polyphenylene sulfone, etc.).
Examples of the material for the ceramic substrate include alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide, and the like.
Examples of the glass substrate material include soda glass, potash glass, borosilicate glass, quartz glass, aluminum silicate glass, and lead glass.
<ゲート電極、ソース電極、ドレイン電極>
ゲート電極、ソース電極、ドレイン電極の材料としては、例えば、金(Au)、銀、アルミニウム(Al)、銅、クロム、ニッケル、コバルト、チタン、白金、タンタル、マグネシウム、カルシウム、バリウム、ナトリウム等の金属;InO2、SnO2、酸化インジウムスズ(ITO)等の導電性の酸化物;ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン、ポリジアセチレン等の導電性高分子;シリコン、ゲルマニウム、ガリウム砒素等の半導体;フラーレン、カーボンナノチューブ、グラファイト等の炭素材料などが挙げられる。中でも、金属であることが好ましく、銀又はアルミニウムであることがより好ましい。
ゲート電極、ソース電極、ドレイン電極の厚みは特に制限されないが、20〜200nmであることが好ましい。<Gate electrode, source electrode, drain electrode>
Examples of materials for the gate electrode, the source electrode, and the drain electrode include gold (Au), silver, aluminum (Al), copper, chromium, nickel, cobalt, titanium, platinum, tantalum, magnesium, calcium, barium, and sodium. Metal: conductive oxide such as InO 2 , SnO 2 , indium tin oxide (ITO); conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, polydiacetylene; semiconductor such as silicon, germanium, gallium arsenide; fullerene And carbon materials such as carbon nanotubes and graphite. Among these, a metal is preferable, and silver or aluminum is more preferable.
The thickness of the gate electrode, source electrode, and drain electrode is not particularly limited, but is preferably 20 to 200 nm.
ゲート電極、ソース電極、ドレイン電極を形成する方法は特に制限されないが、例えば、基板上に、電極材料を真空蒸着又はスパッタする方法、電極形成用組成物を塗布又は印刷する方法などが挙げられる。また、電極をパターニングする場合、パターニングする方法としては、例えば、フォトリソグラフィー法;インクジェット印刷、スクリーン印刷、オフセット印刷、凸版印刷等の印刷法;マスク蒸着法などが挙げられる。 The method for forming the gate electrode, the source electrode, and the drain electrode is not particularly limited, and examples thereof include a method of vacuum-depositing or sputtering an electrode material on a substrate, and a method of applying or printing an electrode-forming composition. In the case of patterning the electrode, examples of the patterning method include a photolithography method; a printing method such as ink jet printing, screen printing, offset printing, letterpress printing; and a mask vapor deposition method.
<ゲート絶縁膜>
ゲート絶縁膜の材料としては、ポリメチルメタクリレート、ポリスチレン、ポリビニルフェノール、ポリイミド、ポリカーボネート、ポリエステル、ポリビニルアルコール、ポリ酢酸ビニル、ポリウレタン、ポリスルホン、ポリベンゾキサゾール、ポリシルセスキオキサン、エポキシ樹脂、フェノール樹脂等のポリマー;二酸化珪素、酸化アルミニウム、酸化チタン等の酸化物;窒化珪素等の窒化物などが挙げられる。これらの材料のうち、有機半導体膜との相性から、ポリマーであることが好ましい。
ゲート絶縁膜の材料としてポリマーを用いる場合、架橋剤(例えば、メラミン)を併用することが好ましい。架橋剤を併用することで、ポリマーが架橋されて、形成されるゲート絶縁膜の耐久性が向上する。
ゲート絶縁膜の膜厚は特に制限されないが、100〜1,000nmであることが好ましい。<Gate insulation film>
Materials for the gate insulating film include polymethyl methacrylate, polystyrene, polyvinyl phenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, epoxy resin, phenol resin And the like; oxides such as silicon dioxide, aluminum oxide, and titanium oxide; and nitrides such as silicon nitride. Of these materials, a polymer is preferable in view of compatibility with the organic semiconductor film.
When a polymer is used as the material for the gate insulating film, it is preferable to use a crosslinking agent (for example, melamine) in combination. By using a crosslinking agent in combination, the polymer is crosslinked and the durability of the formed gate insulating film is improved.
The thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1,000 nm.
ゲート絶縁膜を形成する方法は特に制限されないが、例えば、ゲート電極が形成された基板上に、ゲート絶縁膜形成用組成物を塗布する方法、ゲート絶縁膜材料を蒸着又はスパッタする方法などが挙げられる。ゲート絶縁膜形成用組成物を塗布する方法は特に制限されず、公知の方法(バーコート法、スピンコート法、ナイフコート法、ドクターブレード法)を使用することができる。
ゲート絶縁膜形成用組成物を塗布してゲート絶縁膜を形成する場合、溶媒除去、架橋などを目的として、塗布後に加熱(ベーク)してもよい。The method for forming the gate insulating film is not particularly limited, and examples thereof include a method of applying a composition for forming a gate insulating film on a substrate on which a gate electrode is formed, and a method of depositing or sputtering a gate insulating film material. It is done. The method for applying the gate insulating film forming composition is not particularly limited, and known methods (bar coating method, spin coating method, knife coating method, doctor blade method) can be used.
When a gate insulating film forming composition is applied to form a gate insulating film, it may be heated (baked) after application for the purpose of solvent removal, crosslinking, and the like.
<有機半導体膜>
本発明の有機半導体膜は、本発明の有機半導体膜形成用組成物より形成される膜である。
有機半導体膜の形成方法は特に制限されず、上述した組成物を、ソース電極、ドレイン電極、及び、ゲート絶縁膜上に付与して、必要に応じて乾燥処理を施すことにより、所望の有機半導体膜を形成することができる。<Organic semiconductor film>
The organic semiconductor film of the present invention is a film formed from the composition for forming an organic semiconductor film of the present invention.
The method for forming the organic semiconductor film is not particularly limited, and the above-described composition is applied on the source electrode, the drain electrode, and the gate insulating film, and is subjected to a drying treatment as necessary, thereby obtaining a desired organic semiconductor. A film can be formed.
<バインダーポリマー層>
本発明の有機半導体素子は、上記有機半導体層と絶縁膜との間にバインダーポリマー層を有することが好ましく、上記有機半導体層とゲート絶縁膜との間にバインダーポリマー層を有することがより好ましい。上記バインダーポリマー層の膜厚は特に制限されないが、20〜500nmであることが好ましい。上記バインダーポリマー層は、上記ポリマーを含む層であればよいが、上記バインダーポリマーからなる層であることが好ましい。<Binder polymer layer>
The organic semiconductor element of the present invention preferably has a binder polymer layer between the organic semiconductor layer and the insulating film, and more preferably has a binder polymer layer between the organic semiconductor layer and the gate insulating film. The thickness of the binder polymer layer is not particularly limited, but is preferably 20 to 500 nm. Although the said binder polymer layer should just be a layer containing the said polymer, it is preferable that it is a layer which consists of the said binder polymer.
バインダーポリマー層を形成する方法は特に制限されないが、公知の方法(バーコート法、スピンコート法、ナイフコート法、ドクターブレード法、インクジェット法)を使用することができる。
バインダーポリマー層形成用組成物を塗布してバインダーポリマー層を形成する場合、溶媒除去、架橋などを目的として、塗布後に加熱(ベーク)してもよい。The method for forming the binder polymer layer is not particularly limited, and a known method (bar coating method, spin coating method, knife coating method, doctor blade method, ink jet method) can be used.
When a binder polymer layer forming composition is applied to form a binder polymer layer, it may be heated (baked) after application for the purpose of solvent removal, crosslinking and the like.
<封止層>
本発明の有機半導体素子は、耐久性の観点から、最外層に封止層を備えることが好ましい。封止層には公知の封止剤を用いることができる。
封止層の厚さは特に制限されないが、0.2〜10μmであることが好ましい。<Sealing layer>
The organic semiconductor element of the present invention preferably includes a sealing layer as the outermost layer from the viewpoint of durability. A well-known sealing agent can be used for a sealing layer.
The thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.
封止層を形成する方法は特に制限されないが、例えば、ゲート電極とゲート絶縁膜とソース電極とドレイン電極と有機半導体膜とが形成された基板上に、封止層形成用組成物を塗布する方法などが挙げられる。封止層形成用組成物を塗布する方法の具体例は、ゲート絶縁膜形成用組成物を塗布する方法と同じである。封止層形成用組成物を塗布して有機半導体膜を形成する場合、溶媒除去、架橋などを目的として、塗布後に加熱(ベーク)してもよい。 The method for forming the sealing layer is not particularly limited. For example, the composition for forming the sealing layer is applied onto the substrate on which the gate electrode, the gate insulating film, the source electrode, the drain electrode, and the organic semiconductor film are formed. Methods and the like. A specific example of the method of applying the sealing layer forming composition is the same as the method of applying the gate insulating film forming composition. When an organic semiconductor film is formed by applying the sealing layer forming composition, it may be heated (baked) after application for the purpose of solvent removal, crosslinking and the like.
また、図2は、本発明の有機半導体素子(有機薄膜トランジスタ)の別の一態様の断面模式図である。
図2において、有機薄膜トランジスタ200は、基板10と、基板10上に配置されたゲート電極20と、ゲート電極20を覆うゲート絶縁膜30と、ゲート絶縁膜30上に配置された有機半導体膜50と、有機半導体膜50上に配置されたソース電極40及びドレイン電極42と、各部材を覆う封止層60を備える。ここで、ソース電極40及びドレイン電極42は、上述した本発明の組成物を用いて形成されたものである。有機薄膜トランジスタ200は、ボトムゲート−トップコンタクト型の有機薄膜トランジスタである。
基板、ゲート電極、ゲート絶縁膜、ソース電極、ドレイン電極、有機半導体膜及び封止層については、上述のとおりである。FIG. 2 is a schematic cross-sectional view of another embodiment of the organic semiconductor element (organic thin film transistor) of the present invention.
2, the organic thin film transistor 200 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and an organic semiconductor film 50 disposed on the gate insulating film 30. A source electrode 40 and a drain electrode 42 disposed on the organic semiconductor film 50 and a sealing layer 60 covering each member are provided. Here, the source electrode 40 and the drain electrode 42 are formed using the composition of the present invention described above. The organic thin film transistor 200 is a bottom gate-top contact type organic thin film transistor.
The substrate, gate electrode, gate insulating film, source electrode, drain electrode, organic semiconductor film, and sealing layer are as described above.
上記では図1及び図2において、ボトムゲート−ボトムコンタクト型の有機薄膜トランジスタ、及び、ボトムゲート−トップコンタクト型の有機薄膜トランジスタの態様について詳述したが、本発明の有機半導体素子は、トップゲート−ボトムコンタクト型の有機薄膜トランジスタ、及び、トップゲート−トップコンタクト型の有機薄膜トランジスタにも好適に使用できる。
なお、上述した有機薄膜トランジスタは、電子ペーパー、ディスプレイデバイスなどに好適に使用できる。1 and 2, the embodiments of the bottom gate-bottom contact type organic thin film transistor and the bottom gate-top contact type organic thin film transistor have been described in detail. It can also be suitably used for contact type organic thin film transistors and top gate-top contact type organic thin film transistors.
In addition, the organic thin-film transistor mentioned above can be used conveniently for electronic paper, a display device, etc.
(有機半導体膜形成用組成物)
本発明の有機半導体膜形成用組成物は、特定有機半導体化合物、及び、溶媒を含有することを特徴とする。
また、本発明の有機半導体膜形成用組成物は、バインダーポリマーを含有することが好ましい。
本発明の有機半導体膜形成用組成物における特定有機半導体化合物、バインダーポリマー及び溶媒は、上述した特定有機半導体化合物、バインダーポリマー及び溶媒と同義であり、好ましい態様も同様である。(Composition for forming an organic semiconductor film)
The composition for forming an organic semiconductor film of the present invention is characterized by containing a specific organic semiconductor compound and a solvent.
Moreover, it is preferable that the composition for organic-semiconductor film formation of this invention contains a binder polymer.
The specific organic semiconductor compound, the binder polymer, and the solvent in the composition for forming an organic semiconductor film of the present invention have the same meanings as the specific organic semiconductor compound, the binder polymer, and the solvent described above, and preferred embodiments are also the same.
本発明の有機半導体膜形成用組成物は、特定有機半導体化合物及びバインダーポリマー以外に他の成分を含んでいてもよい。
その他の成分としては、公知の添加剤等を用いることができる。
本発明の有機半導体膜形成用組成物における特定有機半導体化合物及びバインダーポリマー以外の成分の含有量は、有機半導体膜形成用組成物の全固形分に対し、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、1質量%以下であることが更に好ましく、0.1質量%以下であることが特に好ましい。上記範囲であると、膜形成性に優れ、得られる有機半導体の移動度及び熱安定性により優れる。なお、固形分とは、溶媒等の揮発性成分を除いた成分の量である。The composition for forming an organic semiconductor film of the present invention may contain other components in addition to the specific organic semiconductor compound and the binder polymer.
As other components, known additives and the like can be used.
The content of the components other than the specific organic semiconductor compound and the binder polymer in the composition for forming an organic semiconductor film of the present invention is preferably 10% by mass or less based on the total solid content of the composition for forming an organic semiconductor film, It is more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. When it is in the above range, the film-forming property is excellent, and the mobility and thermal stability of the obtained organic semiconductor are excellent. In addition, solid content is the quantity of the component except volatile components, such as a solvent.
本発明の有機半導体膜形成用組成物の粘度は、特に制限されないが、塗布性がより優れる点で、3〜100mPa・sが好ましく、5〜50mPa・sがより好ましく、9〜40mPa・sが更に好ましい。なお、本発明における粘度は、25℃での粘度である。
粘度の測定方法としては、JIS Z8803に準拠した測定方法であることが好ましい。The viscosity of the composition for forming an organic semiconductor film of the present invention is not particularly limited, but is preferably 3 to 100 mPa · s, more preferably 5 to 50 mPa · s, and more preferably 9 to 40 mPa · s in terms of more excellent coating properties. Further preferred. In addition, the viscosity in this invention is a viscosity in 25 degreeC.
As a measuring method of a viscosity, it is preferable that it is a measuring method based on JISZ8803.
本発明の有機半導体膜形成用組成物の製造方法は、特に制限されず、公知の方法を採用できる。例えば、溶媒中に所定量の特定有機半導体化合物を添加して、適宜撹拌処理を施すことにより、所望の組成物を得ることができる。また、バインダーポリマーを用いる場合は、特定有機半導体化合物及びバインダーポリマーを同時又は逐次に添加して好適に組成物を作製することができる。 The manufacturing method of the composition for forming an organic semiconductor film of the present invention is not particularly limited, and a known method can be adopted. For example, a desired composition can be obtained by adding a predetermined amount of a specific organic semiconductor compound in a solvent and appropriately performing a stirring treatment. Moreover, when using a binder polymer, a specific organic-semiconductor compound and a binder polymer can be added simultaneously or sequentially, and a composition can be produced suitably.
(有機半導体膜)
本発明の有機半導体膜は、特定有機半導体を含有することを特徴とする。
また、本発明の有機半導体膜は、バインダーポリマーを含有することが好ましい。
本発明の有機半導体膜における特定有機半導体化合物、並びに、バインダーポリマーは、本発明の有機半導体素子において上述した特定有機半導体化合物、特定有機半導体化合物を重合することにより得られたポリマー及びオリゴマー、並びに、バインダーポリマーと同義であり、好ましい態様も同様である。(Organic semiconductor film)
The organic semiconductor film of the present invention contains a specific organic semiconductor.
The organic semiconductor film of the present invention preferably contains a binder polymer.
The specific organic semiconductor compound and the binder polymer in the organic semiconductor film of the present invention include the specific organic semiconductor compound described above in the organic semiconductor element of the present invention, a polymer and an oligomer obtained by polymerizing the specific organic semiconductor compound, and It is synonymous with a binder polymer, and its preferable aspect is also the same.
本発明の有機半導体膜形成用組成物は、特定有機半導体化合物、特定有機半導体化合物を重合することにより得られたポリマー及びオリゴマー、並びに、バインダーポリマー以外に他の成分を含んでいてもよい。
その他の成分としては、公知の添加剤等を用いることができる。
本発明の有機半導体膜における特定有機半導体化合物、特定有機半導体化合物を重合することにより得られたポリマー及びオリゴマー、並びに、バインダーポリマー以外の成分の含有量は、有機半導体膜の全質量に対し、10質量%以下であることが好ましく、5質量%以下であることが好ましく、1質量%以下であることが更に好ましく、0.1質量%以下であることが特に好ましい。上記範囲であると、膜形成性に優れ、得られる有機半導体の移動度及び熱安定性により優れる。なお、固形分とは、溶媒等の揮発性成分を除いた成分の量である。The composition for forming an organic semiconductor film of the present invention may contain other components in addition to the specific organic semiconductor compound, the polymer and oligomer obtained by polymerizing the specific organic semiconductor compound, and the binder polymer.
As other components, known additives and the like can be used.
The specific organic semiconductor compound in the organic semiconductor film of the present invention, the polymer and oligomer obtained by polymerizing the specific organic semiconductor compound, and the content of components other than the binder polymer are 10 with respect to the total mass of the organic semiconductor film. It is preferably at most mass%, preferably at most 5 mass%, more preferably at most 1 mass%, particularly preferably at most 0.1 mass%. When it is in the above range, the film-forming property is excellent, and the mobility and thermal stability of the obtained organic semiconductor are excellent. In addition, solid content is the quantity of the component except volatile components, such as a solvent.
本発明の有機半導体膜の膜厚は、特に制限されないが、得られる有機半導体の移動度及び熱安定性の観点から、10〜500nmが好ましく、30〜200nmがより好ましい。
本発明の有機半導体膜は、有機半導体素子に好適に使用することができ、有機トランジスタ(有機薄膜トランジスタ)に特に好適に使用することができる。
本発明の有機半導体膜は、本発明の有機半導体膜形成用組成物を用いて好適に作製することができる。Although the film thickness of the organic-semiconductor film of this invention is not restrict | limited in particular, 10-500 nm is preferable and 30-200 nm is more preferable from a viewpoint of the mobility and thermal stability of the organic semiconductor obtained.
The organic semiconductor film of the present invention can be suitably used for an organic semiconductor element, and can be particularly suitably used for an organic transistor (organic thin film transistor).
The organic semiconductor film of the present invention can be suitably produced using the composition for forming an organic semiconductor film of the present invention.
以下に実施例を挙げて本発明を更に具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。なお、特に断りのない限り、「部」、「%」は質量基準である。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.
(有機半導体化合物)
有機半導体層に用いた有機半導体化合物である、E−1〜E−6は、上記有機半導体化合物の具体例として記載したE−1〜E−6と同様である。
また、比較化合物C−1〜C−4の構造を以下に示す。(Organic semiconductor compound)
E-1 to E-6, which are organic semiconductor compounds used in the organic semiconductor layer, are the same as E-1 to E-6 described as specific examples of the organic semiconductor compound.
Moreover, the structure of comparative compound C-1 to C-4 is shown below.
<化合物の合成>
化合物E−1は以下に示す合成スキームで合成した。具体的には、J.Mater.Chem.,2012,22,14639.、特開2011−168747号公報、Macromol.,2013,46,3887.及びJ.Org.Chem.1985,50,1681.を参考に、下記スキームに従い、合成中間体IMを合成した。
合成中間体IM(235mg,0.298mmol)、2,5−ビス(トリメチルスタニル)チエノ[3,2−b]チオフェン(東京化成工業(株)製、139mg,0.298mol)、トリ(o−トリル)ホスフィン(和光純薬工業(株)製、18mg,0.06mmol)、トリス(ジベンジリデンアセトン)ジパラジウム(東京化成工業(株)製、14mg,0.015mmol)、脱水トルエン(和光純薬工業(株)製、15mL)を混合し、窒素雰囲気下、100℃で60時間撹拌した。反応液を室温まで冷却した後、メタノールを300mL添加し、2時間撹拌した。析出物をろ過、メタノール洗浄した後、メタノール、アセトン、ヘキサン、ジクロロメタン、クロロホルムで順次ソックスレー抽出し、可溶性の不純物を取り除いた。続いて、ジクロロベンゼンでソックスレー抽出し、溶液を減圧濃縮した後、メタノールを添加し、析出した固形分をろ過、メタノール洗浄することにより、化合物1を176mg得た(収率77%)。
化合物E−2〜E−6も化合物E−1に準じた方法で合成した。<Synthesis of compounds>
Compound E-1 was synthesized by the following synthesis scheme. Specifically, J. et al. Mater. Chem. 2012, 22, 14639. JP, 2011-168747, Macromol. , 2013, 46, 3887. And J.A. Org. Chem. 1985, 50, 1681. The synthesis intermediate IM was synthesized according to the following scheme.
Synthetic intermediate IM (235 mg, 0.298 mmol), 2,5-bis (trimethylstannyl) thieno [3,2-b] thiophene (manufactured by Tokyo Chemical Industry Co., Ltd., 139 mg, 0.298 mol), tri (o -Tolyl) phosphine (manufactured by Wako Pure Chemical Industries, 18 mg, 0.06 mmol), tris (dibenzylideneacetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd., 14 mg, 0.015 mmol), dehydrated toluene (Wako Pure) Yaku Kogyo Co., Ltd., 15 mL) was mixed and stirred at 100 ° C. for 60 hours under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, 300 mL of methanol was added and stirred for 2 hours. The precipitate was filtered and washed with methanol, and then Soxhlet extracted with methanol, acetone, hexane, dichloromethane and chloroform in order to remove soluble impurities. Subsequently, after Soxhlet extraction with dichlorobenzene and concentration of the solution under reduced pressure, methanol was added, and the precipitated solid was filtered and washed with methanol to obtain 176 mg of Compound 1 (yield 77%).
Compounds E-2 to E-6 were also synthesized by a method according to Compound E-1.
比較化合物C−1は特表2010−527327号公報に記載の化合物である。
比較化合物C−2はMacromol.,2013,46,3887.に記載の化合物P3である。
比較化合物C−3及びC−4はJ.Phys.Chem.C,2014,118,3953.に記載の化合物TPD−Th−S及び化合物TPD−Fu−Sである。
化合物E−1〜E−6及び、比較化合物C−1〜C−4はいずれも、高速液体クロマトグラフィー(東ソー(株)製、TSKgel ODS−100Z)により純度(254nmの吸収強度面積比)が99.8%以上であることを確認した。Comparative compound C-1 is a compound described in JP-T-2010-527327.
Comparative compound C-2 was obtained from Macromol. , 2013, 46, 3887. It is compound P3 as described in above.
Comparative compounds C-3 and C-4 are described in J. Org. Phys. Chem. C, 2014, 118, 3953. Compound TPD-Th-S and Compound TPD-Fu-S described in 1.
Compounds E-1 to E-6 and comparative compounds C-1 to C-4 are both high in purity (254 nm absorption intensity area ratio) by high performance liquid chromatography (manufactured by Tosoh Corporation, TSKgel ODS-100Z). It was confirmed that it was 99.8% or more.
<使用した出発原料>
化合物E−1の合成に使用した3,4−チオフェンジカルボン酸無水物は、東京化成工業(株)より購入した。<Starting materials used>
3,4-thiophenedicarboxylic anhydride used for the synthesis of compound E-1 was purchased from Tokyo Chemical Industry Co., Ltd.
<その他使用試薬>
2−n−オクチル−1−ドデシルアミン(東京化成工業(株)製)
トリメチル(2−チエニル)すず(和光純薬工業(株)製)
NBS:N−ブロモスクシンイミド(和光純薬工業(株)製)
ローソン試薬(和光純薬工業(株)製)<Other reagents used>
2-n-octyl-1-dodecylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Trimethyl (2-thienyl) tin (manufactured by Wako Pure Chemical Industries, Ltd.)
NBS: N-bromosuccinimide (manufactured by Wako Pure Chemical Industries, Ltd.)
Lawson Reagent (Wako Pure Chemical Industries, Ltd.)
<バインダーポリマー>
バインダーとして用いたポリマーを以下に示す。
PαMS:ポリ−α−メチルスチレン、重量平均分子量437,000、シグマアルドリッチ社製
PTAA:ポリ[ビス(4−フェニル)(2,4,6−トリメチルフェニル)アミン]、数平均分子量7,000〜10,000、シグマアルドリッチ社製
PCPDTBT:ポリ[2,6−(4,4−ビス(2−エチルヘキシル)−4Hシクロペンタ[2,1−b;3,4−b’]ジチオフェン)−アルト−4,7−(2,1,3−ベンゾチアジアゾール)]、重量平均分子量7,000〜20,000、シグマアルドリッチ社製<Binder polymer>
The polymer used as the binder is shown below.
PαMS: poly-α-methylstyrene, weight average molecular weight 437,000, manufactured by Sigma-Aldrich Corporation PTAA: poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine], number average molecular weight 7,000 to 10,000, Sigma-Aldrich PCPDTBT: Poly [2,6- (4,4-bis (2-ethylhexyl) -4Hcyclopenta [2,1-b; 3,4-b ′] dithiophene) -alto-4 , 7- (2,1,3-benzothiadiazole)], weight average molecular weight 7,000 to 20,000, manufactured by Sigma-Aldrich
<有機半導体膜形成用塗布液の調製>
表1に記載の有機半導体化合物(0.5質量%)/バインダーポリマー(表1に記載の濃度)/アニソール(沸点154℃)を硝子バイヤルに秤量し、ミックスローター(アズワン(株)製)で10分間撹拌混合した後、0.5μmメンブレンフィルターでろ過することで、有機半導体膜形成用塗布液(有機半導体膜形成用組成物)を得た。表1中、バインダーポリマーが「−」と記載されているものはバインダーポリマーを添加していないことを示す。
なお、表1中、括弧内に記載したバインダーポリマーの濃度は、塗布液中の質量%である。<Preparation of coating solution for organic semiconductor film formation>
The organic semiconductor compound (0.5% by mass) / binder polymer (concentration described in Table 1) / anisole (boiling point 154 ° C.) listed in Table 1 was weighed into a glass vial and mixed rotor (manufactured by ASONE Co., Ltd.). After stirring and mixing for 10 minutes, the coating solution for forming an organic semiconductor film (composition for forming an organic semiconductor film) was obtained by filtering with a 0.5 μm membrane filter. In Table 1, the case where the binder polymer is described as “-” indicates that the binder polymer is not added.
In Table 1, the concentration of the binder polymer described in parentheses is mass% in the coating solution.
<TFT素子作製>
ガラス基板(イーグルXG:コーニング社製)上に、ゲート電極となるAlを蒸着した(厚み:50nm)。その上にゲート絶縁膜形成用組成物(ポリビニルフェノール/メラミン=1質量部/1質量部(w/w)のPGMEA(プロピレングリコールモノメチルエーテルアセテート)溶液(固形分濃度:2質量%))をスピンコートし、150℃で60分間ベークを行うことで膜厚400nmのゲート絶縁膜を形成した。その上に銀インク(H−1、三菱マテリアル(株)製)をインクジェット装置DMP−2831(富士フイルムダイマティクス社製)を用いてソース電極及びドレイン電極状(チャネル長40μm、チャネル幅200μm)に描画した。その後オーブンにて180℃、30分間ベークを行い、焼結して、ソース電極及びドレイン電極を形成することでTFT特性評価用素子基板を得た。
TFT特性評価用素子基板の上に各有機半導体膜形成用塗布液をスピンコート(500rpm、10秒間の後1,000rpm、30秒間)した後、ホットプレート上で50℃10分間、又は180℃10分間乾燥(アニール)することにより有機半導体層を形成し、ボトムゲートボトムコンタクト型の有機TFT素子を得た。<TFT device fabrication>
Al serving as a gate electrode was deposited on a glass substrate (Eagle XG: Corning) (thickness: 50 nm). On top of that, a composition for forming a gate insulating film (polyvinylphenol / melamine = 1 part by weight / 1 part by weight (w / w) PGMEA (propylene glycol monomethyl ether acetate) solution (solid content concentration: 2% by weight)) is spun A gate insulating film having a thickness of 400 nm was formed by coating and baking at 150 ° C. for 60 minutes. On top of that, silver ink (H-1, manufactured by Mitsubishi Materials Corporation) is formed into a source electrode and a drain electrode (channel length: 40 μm, channel width: 200 μm) using an inkjet device DMP-2831 (manufactured by Fujifilm Dimatics). Drawn. Thereafter, baking was performed at 180 ° C. for 30 minutes in an oven, sintering was performed, and a source electrode and a drain electrode were formed to obtain an element substrate for TFT characteristic evaluation.
Each organic semiconductor film-forming coating solution is spin-coated on the element substrate for TFT characteristic evaluation (500 rpm, 10 seconds, then 1,000 rpm, 30 seconds), and then on a hot plate at 50 ° C. for 10 minutes, or 180 ° C. 10 By drying (annealing) for a minute, an organic semiconductor layer was formed, and a bottom gate bottom contact type organic TFT element was obtained.
<特性評価>
半導体特性評価装置B2900A(アジレント・テクノロジー(株)製)を用い、大気下で以下の性能評価を行った。
(a)キャリア移動度、及び、(b)移動度バラツキ
各有機TFT素子のソース電極−ドレイン電極間に、−60Vの電圧を印加し、ゲート電圧を+10V〜−60Vの範囲で変化させ、ドレイン電流Idを表す下記式を用いてキャリア移動度μを算出した。
Id=(w/2L)μCi(Vg−Vth)2
式中、Lはゲート長、wはゲート幅、Ciは絶縁層の単位面積当たりの容量、Vgはゲート電圧、Vthは閾値電圧を表す。
表1中に示すキャリア移動度の値は、10素子の平均値である。キャリア移動度μは高いほど好ましく、実用上は1.0×10-2cm2/Vs以上であることが好ましく、1.0×10-1cm2/Vs以上であることがより好ましい。なお、移動度が1.0×10-5cm2/Vsを下回るものに関しては特性が低すぎるため、表中には「<1.0×10-5」と記載し、以下の評価は行わなかった。
また、10素子のキャリア移動度に対して以下の式で計算した変異係数を、以下の5段階で評価し、移動度バラツキの指標として用いた。この値が小さいほど素子間の移動度バラツキが小さいことを示す。実用上、A又はBであることが好ましく、Aであることがより好ましい。
変異係数=標準偏差÷平均値×100
A:15%未満
B:15%以上30%未満
C:30%以上50%未満
D:50%以上<Characteristic evaluation>
The following performance evaluation was performed under the atmosphere using a semiconductor characteristic evaluation apparatus B2900A (manufactured by Agilent Technologies).
(A) Carrier mobility, and (b) mobility variation A voltage of −60 V is applied between the source electrode and the drain electrode of each organic TFT element, and the gate voltage is changed in the range of +10 V to −60 V, and the drain The carrier mobility μ was calculated using the following formula representing the current I d .
I d = (w / 2L) μC i (V g −V th ) 2
In the formula, L is the gate length, w is the gate width, C i is the capacitance per unit area of the insulating layer, V g is the gate voltage, and V th is the threshold voltage.
The value of carrier mobility shown in Table 1 is an average value of 10 elements. The carrier mobility μ is preferably as high as possible. Practically, it is preferably 1.0 × 10 −2 cm 2 / Vs or more, and more preferably 1.0 × 10 −1 cm 2 / Vs or more. In addition, since the characteristics are too low for those whose mobility is less than 1.0 × 10 −5 cm 2 / Vs, “<1.0 × 10 −5 ” is described in the table, and the following evaluation is performed. There wasn't.
In addition, the variation coefficient calculated by the following formula for the carrier mobility of 10 elements was evaluated in the following 5 stages and used as an index of mobility variation. It shows that the mobility variation between elements is so small that this value is small. Practically, it is preferably A or B, more preferably A.
Variation coefficient = standard deviation ÷ average value x 100
A: Less than 15% B: 15% or more and less than 30% C: 30% or more and less than 50% D: 50% or more
10:基板、20:ゲート電極、30:ゲート絶縁膜、40:ソース電極、42:ドレイン電極、50:有機半導体膜、60:封止層、100,200:有機薄膜トランジスタ 10: substrate, 20: gate electrode, 30: gate insulating film, 40: source electrode, 42: drain electrode, 50: organic semiconductor film, 60: sealing layer, 100, 200: organic thin film transistor
Claims (19)
有機半導体素子。
式1中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、R 11は一価の有機基を表し、Ar11、Ar12、Ar13はそれぞれ独立に、芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m11は0〜2の整数を表し、m12は0〜4の整数を表し、m13は0〜2の整数を表し、m11とm12とm13の合計は1以上である。 It has an organic semiconductor layer containing an organic semiconductor having a repeating unit represented by Formula 1,
Organic semiconductor element.
In Formula 1, X represents any of CR 12 2 , O, S, Se, NR 12 , SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents S 1 , N—CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13 . , R 13 represents a monovalent organic group, a plurality of R 13 may combine with each other to form a ring , R 11 represents a monovalent organic group, and Ar 11 , Ar 12 , and Ar 13 each represent Independently, it represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m11 represents an integer of 0 to 2, m12 represents an integer of 0 to 4, and m13 represents 0 to 2 integer Represents the sum of m11 and m12 and m13 is 1 or more.
式2中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、R 11は一価の有機基を表し、Ar12は芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m12は0〜4の整数を表し、X21及びX22はそれぞれ独立に、O、S、Se、NR12’、SiR12’ 2のいずれかを表し、R12’はそれぞれ独立に、水素原子又は一価の有機基を表し、R21〜R24はそれぞれ独立に、水素原子又は一価の有機基を表し、m11’は0〜2の整数を表し、m13’は0〜2の整数を表し、m11’とm12とm13’の合計は1以上である。 The organic-semiconductor element of any one of Claims 1-3 whose repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.
In Formula 2, X represents any of CR 12 2 , O, S, Se, NR 12 , and SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents S 1 , N—CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13 . , R 13 represents a monovalent organic group, a plurality of R 13 may combine with each other to form a ring , R 11 represents a monovalent organic group, Ar 12 represents an aromatic hydrocarbon group, aromatic Represents a group heterocyclic group, vinylene group or ethynylene group, m12 represents an integer of 0 to 4, and X 21 and X 22 each independently represents O, S, Se, NR 12 ′ , or SiR 12 ′ 2 . Table represents either, on the R 12 'each independently represents a hydrogen atom or a monovalent organic group, R 21 to R 24 are each independently, a hydrogen atom or a monovalent organic group , M11 'represents an integer of 0 to 2, m13' will table an integer of 0 to 2, the sum of m11 'and m12 and m13' is 1 or more.
式1中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、R 11は一価の有機基を表し、Ar11、Ar12、Ar13はそれぞれ独立に、芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m11は0〜2の整数を表し、m12は0〜4の整数を表し、m13は0〜2の整数を表し、m11とm12とm13の合計は1以上である。 A compound having a repeating unit represented by Formula 1.
In Formula 1, X represents any of CR 12 2 , O, S, Se, NR 12 , SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents S 1 , N—CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13 . , R 13 represents a monovalent organic group, a plurality of R 13 may combine with each other to form a ring , R 11 represents a monovalent organic group, and Ar 11 , Ar 12 , and Ar 13 each represent Independently, it represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m11 represents an integer of 0 to 2, m12 represents an integer of 0 to 4, and m13 represents 0 to 2 integer Represents the sum of m11 and m12 and m13 is 1 or more.
式2中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、R 11は一価の有機基を表し、Ar12は芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m12は0〜4の整数を表し、X21及びX22はそれぞれ独立に、O、S、Se、NR12’、SiR12’ 2のいずれかを表し、R12’はそれぞれ独立に、水素原子又は一価の有機基を表し、R21〜R24はそれぞれ独立に、水素原子又は一価の有機基を表し、m11’は0〜2の整数を表し、m13’は0〜2の整数を表し、m11’とm12とm13’の合計は1以上である。 The compound according to any one of claims 5 to 7, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.
In Formula 2, X represents any of CR 12 2 , O, S, Se, NR 12 , and SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents S 1 , N—CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13 . , R 13 represents a monovalent organic group, a plurality of R 13 may combine with each other to form a ring , R 11 represents a monovalent organic group, Ar 12 represents an aromatic hydrocarbon group, aromatic Represents a group heterocyclic group, vinylene group or ethynylene group, m12 represents an integer of 0 to 4, and X 21 and X 22 each independently represents O, S, Se, NR 12 ′ , or SiR 12 ′ 2 . Table represents either, on the R 12 'each independently represents a hydrogen atom or a monovalent organic group, R 21 to R 24 are each independently, a hydrogen atom or a monovalent organic group , M11 'represents an integer of 0 to 2, m13' will table an integer of 0 to 2, the sum of m11 'and m12 and m13' is 1 or more.
式1中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、R 11は一価の有機基を表し、Ar11、Ar12、Ar13はそれぞれ独立に、芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m11は0〜2の整数を表し、m12は0〜4の整数を表し、m13は0〜2の整数を表し、m11とm12とm13の合計は1以上である。 The composition for organic-semiconductor film formation containing the compound which has a repeating unit represented by Formula 1, and a solvent.
In Formula 1, X represents any of CR 12 2 , O, S, Se, NR 12 , SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents S 1 , N—CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13 . , R 13 represents a monovalent organic group, a plurality of R 13 may combine with each other to form a ring , R 11 represents a monovalent organic group, and Ar 11 , Ar 12 , and Ar 13 each represent Independently, it represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m11 represents an integer of 0 to 2, m12 represents an integer of 0 to 4, and m13 represents 0 to 2 integer Represents the sum of m11 and m12 and m13 is 1 or more.
式2中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、R 11は一価の有機基を表し、Ar12は芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m12は0〜4の整数を表し、X21及びX22はそれぞれ独立に、O、S、Se、NR12’、SiR12’ 2のいずれかを表し、R12’はそれぞれ独立に、水素原子又は一価の有機基を表し、R21〜R24はそれぞれ独立に、水素原子又は一価の有機基を表し、m11’は0〜2の整数を表し、m13’は0〜2の整数を表し、m11’とm12とm13’の合計は1以上である。 The composition for organic-semiconductor film formation of any one of Claims 10-12 whose repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.
In Formula 2, X represents any of CR 12 2 , O, S, Se, NR 12 , and SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents S 1 , N—CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13 . , R 13 represents a monovalent organic group, a plurality of R 13 may combine with each other to form a ring , R 11 represents a monovalent organic group, Ar 12 represents an aromatic hydrocarbon group, aromatic Represents a group heterocyclic group, vinylene group or ethynylene group, m12 represents an integer of 0 to 4, and X 21 and X 22 each independently represents O, S, Se, NR 12 ′ , or SiR 12 ′ 2 . Table represents either, on the R 12 'each independently represents a hydrogen atom or a monovalent organic group, R 21 to R 24 are each independently, a hydrogen atom or a monovalent organic group , M11 'represents an integer of 0 to 2, m13' will table an integer of 0 to 2, the sum of m11 'and m12 and m13' is 1 or more.
式1中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、R 11は一価の有機基を表し、Ar11、Ar12、Ar13はそれぞれ独立に、芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m11は0〜2の整数を表し、m12は0〜4の整数を表し、m13は0〜2の整数を表し、m11とm12とm13の合計は1以上である。 An organic semiconductor film containing a compound having a repeating unit represented by Formula 1.
In Formula 1, X represents any of CR 12 2 , O, S, Se, NR 12 , SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents S 1 , N—CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13 . , R 13 represents a monovalent organic group, a plurality of R 13 may combine with each other to form a ring , R 11 represents a monovalent organic group, and Ar 11 , Ar 12 , and Ar 13 each represent Independently, it represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m11 represents an integer of 0 to 2, m12 represents an integer of 0 to 4, and m13 represents 0 to 2 integer Represents the sum of m11 and m12 and m13 is 1 or more.
式2中、XはCR12 2、O、S、Se、NR12、SiR12 2のいずれかを表し、R12はそれぞれ独立に、水素原子又は一価の有機基を表し、Y11及びY12はそれぞれ独立に、S、N−CN、又は、CQ2を表し、QはCN、CF3、C(=O)R13、C(=O)OR13、又は、SO2R13を表し、R13は一価の有機基を表し、複数のR13は互いに結合して環を形成してもよく、R 11は一価の有機基を表し、Ar12は芳香族炭化水素基、芳香族複素環基、ビニレン基、又は、エチニレン基を表し、m12は0〜4の整数を表し、X21及びX22はそれぞれ独立に、O、S、Se、NR12’、SiR12’ 2のいずれかを表し、R12’はそれぞれ独立に、水素原子又は一価の有機基を表し、R21〜R24はそれぞれ独立に、水素原子又は一価の有機基を表し、m11’は0〜2の整数を表し、m13’は0〜2の整数を表し、m11’とm12とm13’の合計は1以上である。 The organic semiconductor film according to any one of claims 16 to 18, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.
In Formula 2, X represents any of CR 12 2 , O, S, Se, NR 12 , and SiR 12 2 , R 12 independently represents a hydrogen atom or a monovalent organic group, Y 11 and Y 12 each independently represents S 1 , N—CN, or CQ 2 , and Q represents CN, CF 3 , C (═O) R 13 , C (═O) OR 13 , or SO 2 R 13 . , R 13 represents a monovalent organic group, a plurality of R 13 may combine with each other to form a ring , R 11 represents a monovalent organic group, Ar 12 represents an aromatic hydrocarbon group, aromatic Represents a group heterocyclic group, vinylene group or ethynylene group, m12 represents an integer of 0 to 4, and X 21 and X 22 each independently represents O, S, Se, NR 12 ′ , or SiR 12 ′ 2 . Table represents either, on the R 12 'each independently represents a hydrogen atom or a monovalent organic group, R 21 to R 24 are each independently, a hydrogen atom or a monovalent organic group , M11 'represents an integer of 0 to 2, m13' will table an integer of 0 to 2, the sum of m11 'and m12 and m13' is 1 or more.
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